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Thermodynamic aspects of gas-phase electron attachment to transition metal tris (Beta-diketonate) complexes

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Title:
Thermodynamic aspects of gas-phase electron attachment to transition metal tris (Beta-diketonate) complexes
Creator:
Sharpe, Paul, 1958-
Publication Date:
Language:
English
Physical Description:
vi, 139 leaves : ill. ; 29 cm.

Subjects

Subjects / Keywords:
Anions ( jstor )
Electron attachment ( jstor )
Electronics ( jstor )
Electrons ( jstor )
Energy value ( jstor )
Enthalpy ( jstor )
Entropy ( jstor )
Ions ( jstor )
Ligands ( jstor )
Solvation ( jstor )
Chemistry thesis Ph. D
Complex compounds ( lcsh )
Dissertations, Academic -- Chemistry -- UF
Ketones ( lcsh )
Thermochemistry ( lcsh )
Transition metal compounds ( lcsh )

Notes

Thesis:
Thesis (Ph. D.)--University of Florida, 1990.
Bibliography:
Includes bibliographical references (leaves 130-138).
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Paul Sharpe.

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University of Florida
Holding Location:
University of Florida
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Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
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23725757 ( OCLC )
AHP3867 ( NOTIS )

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Full Text















THERMODYNAMIC ASPECTS OF GAS-PHASE ELECTRON
TO TRANSITION METAL TRIS(BETA-DIKETONATE)







By


PAUL SHARPE
-" a>


ATTACHMENT
COMPLEXES


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL
FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY


UNIVERSITY


OF FLORIDA


1990
^- -.w

















ACKNOWLEDGMENTS


First


I must


thank my research director


Dr. David E.


Richardson


for his


understanding,


guidance


and support


throughout my graduate


career.


Dr. John R.


Eyler


and Dr.


Cliff Watson


also deserve


considerable


recognition


for their many


contributions


useful


discussions,


especially on


help with


the instrumentation.


No dissertation would be complete without


acknowledging


all the


friends


loved-ones


for their


support.


Foremost


in my mind


in this


regard


Stephanie Weinstock,


whose


love


understanding


have been


constant


source of


encouragement


over the


last


two years.


Also,


would


like


to thank my mother,


and my


late


father whom


know would


have been


proud.


Finally,


at the


will


University of


always

Florida


remember my


colleagues


especially Matt,


Casey,


in Graduate


Mike


School


T.M.


greatly


enhanced the enjoyment


of graduate


school


at Florida.


















TABLE OF CONTENTS



pa*e
ACKNOWLEDGMENTS........................................-.-...........-.ii


CHAPTERS


INTRODUCTION.


Overview of Research.
Introduction to Metal


Properties a
Description

EXPERIMENTAL


B-Diketonate C complexes.
G-Dn^ike'/^toateo Complexes.va


nd Applications of Metal
of the FTICR Technique..


PROCEDURES


B-Diketoi


. .. ..1
. .8
nates .......12
............. 18


AND RESULTS


Preparation of
Cnmle ets a


Tris(hexafluoroacetylacetonate)


omphjJa x ...... ............................~
Preparation of Tris(acetylacetonate) Complexes.
Preparation of Ruthenium Tris(B-Diketonates)...
Organic Compounds..............................
Electron Attachment Studies....................
Gas-Phase Spectrophotometry of Cr(hfac)3.......


. .........23
...........25
S .25
...........26
. ..... .. .26
S.......... .37


TERMINOLOGY AND CONVENTIONS
ION THERMOCHEMISTRY......


USED


Introduction.....................
Electron Affinities and Adiabatic
Potentials.....................
Stationary and Thermal Electron C


IN GAS-PHASE


... .. ... .

.... .... ..* ...


...........
Ionization

conventions.


.. ... 39
.. ...........40


INTRAMOLECULAR ENTROPY CHANGES FOR REDOX COUPLES
INVOLVING COMPLEX METAL IONS...........................48


Introduction.......


Statist
of Ga
Redox
Compari
Chang
Metal
The Rel
of Ga


ical


Mechanics Applied


s-Phase
Couple
son of
es for
Comple
ationsh
s-Phase


Intr
s Inv
Solut
Some
xes..
ip Be
Elec


to the Determination


molecular Entropy Changes for
olving Complex Metal Ions........
ion-Phase and Gas-Phase Entropy
Redox Couples Involving Octahedral


....
twee
tron


Mthfae1.- Comnleres...


. .51


.... ..-............................72
n The Free Energy and Enthalpy
Attachment to M(acac)3 and
- a a a a a a a a a a a a a a a -' 80


ABSTRACT......................... .... .. .......... .... *-*.*


.........................48










METAL-LIGAND BOND ENERGIES AND SALVATION ENERGIES
GAS-PHASE TRANSITION METAL TRIS(ACETYLACETONATE
COMPLEXES AND THEIR ANIONS.....................


)
...... ..


Introduction..............................................84
Electron Attachment Energy Relationships.................85
Homolytic and Heterolytic M-0 Bond Enthalpies in
M(acac)3(g) Complexes and M(acac)3"(g) Ions.............90
Relative Solvation Energies of M(acac)3(g)
and M(acac)3" (g)".*....................................99
Relative Solvation Energies of Ru(tfac)3(g) and
Ru(hfac)3 and Their Negative Ions......................108
Conclusions..............................................111


INTERPRETATION OF THE TRENDS ON THE ELECTRON ATTACHMENT
FREE ENERGIES OF THE TRIS(ACETYLACETONATE) AND
TRIS(HEXAFLUOROACETYLACETONATE) COMPLEXES OF THE
METALS Ti-Co USING THE SIMPLE LIGAND FIELD MODEL.......


Introduction.....................................
Thermochemical Relationships and Periodic Trends.
Conclusions......................................


........113
........114
S. ..128


REFERENCES.


BIOGRAPHICAL SKETCH..................................................
















Abstract


of Dissertation


of the University
Requirements


of Florida


Presented


to the Graduate


in Partial


for the Degree of


Doctor


Fulfillment


School
of the


of Philosophy


THERMODYNAMIC ASPECTS OF GAS-PHASE ELECTRON


TO TRANSITION


METAL


TRIS


(BETA-DIKETONATE)


ATTACHMENT
COMPLEXES


Paul S

August


harpe

1990


Chairman:


Major


David E


Department:

Estimations


Richardson,
Chemistry

of the free


Ph.D.


energies


gas-phase electron


attachment


to several


transition metal


tris(8


-diketonate)


complexes


at 350 K are


reported.


compounds


studied


are the tris(acetylacetonate)


complexes


(M(acac)3)


the tris(hexafluoroacetylacetonate)


complexes


M(hfac)3


of the


data


series


for the


of first


row transition metals


ruthenium complexes


Ru(acac)3,'


= Ga Co.


Ru(tfac)3


In addition,


and Ru(hfac)3


are


reported,


first


where


tfac


trifluoroacetylacetonate.


reliable estimations


of thermal


gas-phase


This work


electron


represents

attachment


energies


for a class


of coordination


compounds.


Electron


using


attachment


Fourier transform


free energies

ion cyclotron


for the


complexes


resonance mass


were obtained


spectrometry


(FTICR)


to monitor


charge-transfer


bracketing


and equilibrium


reactions


involving parent


negative


ions


trapped


in a mixture


of two gases.


gas mixture consisted of


a metal


complex


an organic


reference


compound,


for which


the electron


attachment


free


energy


is established


Theoretical


intramolecular


entropy


changes


some


redox


couples


involving


coordination


complex


ions


are estimated


and compared,


where

















electron


thermochemical


attachment


data


energy


energy
cycles


data are combined


that


lead


with


to estimations


other


of the


changes


in heterolytic M-O bond enthalpies


and solvation


free energies.


The observation


acetylacetonate


of charge-transfer


anions


bracketing


reactions


led to the determination of


involving

heterolytic


homolytic

Published


M-0 bond

estimatio


enthalpies

ns of the


for M(acac)3


absolute


neutrals


potential


of the


their al

standard


onions.

hydrogen


electrode


led to estimations


electron attachment


of the


to the complexes


free energy

in several


for solution-phase


solvents.


For


Ru(acac)3,


single


ion solvation


free energy


is estimated,


result


is discussed


comparison


to a


similar


estimation based on a


dielectric


continuum theoretical model.


results of


this


investigation


serve to


illustrate


relative


importance of


changes


in bond energies


and solvation


energies


that


determine


the magnitude of


redox


couples


involving


reduction


of tris(B-


diketonate)


complexes.

















CHAPTER 1
INTRODUCTION



Overview of Research


Many methods


have


been


used


for the determination


of gas-phase


electron attachment


energies


of atoms


and molecules.


These methods


be categorized


into theoretical,


semiempirical


and experimental,


these


various


approaches


have been


reviewed.


1 Although


some


of the


published data on


gas-phase electron


attachment


energies


has been


determined


from


solution-phase


studies


such


as polarography


and reaction


calorimetry,


the majority


experimental methods


that


of the

study


published work


gas-phase


negative


to date


stems


from the


ions directly.


These


methods were actively


developed


during the early


1970s.


Gas-phase


methods


rely


on a ready


source of


ions,


which


is by


far most


easily


accomplished by the


determinations


have


ionization of


been


performed


a gas.

on ions


Hence,


formed


the majority o

from volatile


precursors.


In the case of


metal-containing


compounds,


studies


negative


ions


have been


restricted


to those


formed


from metal


halides,


especially


are


metal


hexafluorides,


all gases or volatile


hexafluorides


have


oxyhalides,

liquids or


received


and carbonyls.


solids.


a great


deal


These


In particular,

of attention.


compounds

transition


It has


long


been


known


that


these


compounds


are the most


highly


oxidizing


compounds


known,


typically


having


electron


affinities


in the


range of


eV to 10 eV.


The majority


of experimental methods


involving


gas-phase


negative


inns


ths


t. l *IJVr- L ]i*si [ I i fl"( i


Is. ewa


k a a -


. a a s2


tn d~tarmi no


the ci orO-rnn


nt-I- nr.hrnonl-


can


4-












energy


an impinging


particle


that


causes


formation


or breakdown


of a negative


ion.


In the atom


impact


method,


beams of


energy


selected


neutral


alkali


atoms


are collided


with


a neutral


target


gas.


translational


energy


dependence of


the alkali


atom beam


is monitored


a function of


the relative


cross


section


for the


formation


of the


parent


anion


of the


target


molecules.


Using


this


method,


Compton


workers


have provided


estimates


for the


electron


affinities


of MoF6,


ReF6,


SeF6,


TeF6


and WF6.


A related method


involves


colliding negative


the negative

endothermic


ions


ions


into


is varied


electron-transfer


a target


gas.


and the threshold


reaction


translational


energy


for the


energy

onset o


is detected by the observation


formation


charge-transfer


transfer.


of product


or may


enthalpy


ions.


ion-molecule


be accompanied by


of formation


atom


of the


reaction may


transfer,


anion


such


of interest


be simple

as proton


can be


determined


from the enthalpies


of formation of


all other


species


involved


in the


reaction,


combined


with


the threshold


value


of the


translational


atomic


energy


and negative


of the negative


ion beams


ion beam.


in these methods


Although


can be


the energy of


controlled


within


a range of


energy of


0.1


, there


are


several


problems


encountered


prominent


in obtaining


are


distribution


accurate electron


sensitivity


of the


of the


translational


attachment


threshold


energies


energies.


energy to

the target


Most


thermal


gas,


weakness


of the


signal


around


the threshold


energy


lack


information on


initial


and final


states


of the neutral


molecules


product

results


ions.


Due to


for electron


the inherent


affinity values


problems


these methods


for transition metal


have


produced


hexafluorides


that


are


in considerable disagreement


For example,


range of


- 1 an~ -nfl


a
- CC 4 n 4-. 1 .. a


- a A~ a -2


A- ~ ~ ~* __ ^ -- _- A- ----A -


co-












the detachment


using photons


an electron


known


from a


energy


negative


generated by


ion,


according to


a laser,


or light


eq 1-1,

source


with monochromator.


+ hv


= AB +e


Photodetachment methods


use a variable


frequency


laser to detach


electron


from the negative


ion AB


threshold


energy


can be


obtained by using


a variety


of physical


methods


that


detect


either the


detached electrons or the


formation


of neutral


molecules


from the


anions


as a function


of photon


flux


and wavelength.


interaction


of the


negative


ions with


the photon


flux


has been


accomplished


in crossed


photon-molecular


beam experiments,


drift


tubes


and in ion traps.


In photoelectron spectroscopy


frequency


of the


photon


source


is fixed and


the energy


spectrum of


the emitted


electrons


is recorded.


For simple molecular


anions,


composed


a few atoms,


the energy


spectrum can be resolved

the detachment process.


into the vi

Determining


brational


transitions


the energy of


accompanying


the ejected


electrons


from the ground


vibrational


states


of the neutral


anion


leads


very


accurate determinations


of the electron


affinity


of molecules.


Using the photoelectron


spectroscopy method,


Lineberger


co-workers


have


determined


the electron


affinities of


several


carbonyl


complexes


Fe and Ni,


which are


in the


range of


0.6 2.4 eV.8'9


A limitation


extending the technique


to high


electron


affinity


compounds


such as


volatile metal


hexafluorides


is that


although


it may


poss


ible


identify


the energy transitions


in the spectra,


producing


a light


source


required wavelength


and flux


impractical


for compounds


such












Since


about


1982,


techniques


in mass


spectrometry that


are


capable


of following


the time


dependence of


ion-molecule


reactions


have


been


used


to determine


the electron


attachment


energies


of polyatomic


molecules.


In these methods


the equilibrium constant


for a gas-phase


charge-transfer


reaction


involving two


neutral


reactants


their


parent


negative


ions


is measured.


These methods


have


therefore been


described


as equilibrium methods.


techniques


in mass


spectrometry


that


have


been


used


for this


purpose


are pulsed


high


pressure mass


spectrometry


(PHPMS)1 0-15


and ion cyclotron


resonance mass


spectrometry


(ICR)


16-19


Electron


attachment


energies


for many


different


organic


compounds


have been


reported,


and values


are


in the


range


of 0.5 3


types


determinations


new


compounds


are reported each


studied


year.


is still


One


of the


expanding


advantages


and many more


of the


equilibrium method


over threshold methods


for determining


electron


attachment


energies


is that


the moleular


ions


formed after


ionization


are cooled


to the


same temperature


as the neutral molecules


from which


they


are


formed,


usually by


a thermalizing


bath


gas.


Electron


attachment


energies


are


therefore obtained


a definite


temperature


be combined with other


attachment


energies


thermochemical


in condensed-phases.


data,


especially


For example,


many


electron

of the


organic


compounds


studied


exhibit


reversible electrochemical


behavior


this


has led to estimates


of the


change


in solvation


energy


solution


phase reduction of


these compounds


14,15,20


A relatively


recent


technique


in mass


spectrometry that


also


capable of


monitoring the


time dependence of


ion-molecule


reactions


versatile


mass


spectrometry


powerful

(FTICR).


Fourier


transform


An important


ion cyclotron


difference


resonance


between FTICR


-A- ~-. -A.- -t. -~


. A












reactions


research


of metal


considers


containing


ion-molecule


compounds.


processes


21-43


Much


of the


involving metal


published

containing


ions


(mostly derived


from organometallic


precursors)


or bare metal


ions


(produced


by techniques


such


as laser


vaporization


of metal


targets)


The bulk of


this work has


centered


on the reactions


of bare metal


ions or


highly


coordinatively unsaturated metal


ions


with


bonds


21-34


Relatively


little


attention


has been


given,


however,


coordinatively


saturated metal


complexes


with non-carbon


donor


ligands,


such


as coordination


complexes


There were two principal


objectives of


the present


work.


first


was


to determine


the free energies of


thermal


electron


attachment


for a series


of coordination


complexes by using the


FTICR


technique,


thereby


extending the established


the determination


of free energies


charge-transfer

of electron at


equilibrium method


tachment


coordination


complexes.


The compounds


studied


in the


present


work were


tris(acetylacetonate)


(M(acac)3)


tris(hexafluoroacetylacetonate)


(M(hfac


complexes


complexes

Ru(acac)3,


of the series of metals M


Ru(hfac)3


and Ru(tfac)3


= Sc


were


- Co and


also


included


(where


tfac


= trifluoroacetylacetonate).


These


complexes


are


pseudo-octahedral


tris


chelate


coordination


complexes


in which


ligands bind


to metal


centers with


oxygen


atom donors.


Estimates


of the


free energies


electron


attachment


for these complexes


were obtained


in the


present


work,


this


represents


the first


reliable determination


of the gas-


phase electron attachment


energies


of coordination


complexes


under


thermal


conditions.


second


objective was


to determine


the changes


average


heterolytic metal-oxygen


(M-O)


bond


energies


that


occur


during


-phase


i












obtained


incorporating the electron


attachment


free


energy


data


complexes


into energy


cycles35


that


relate


the energy


for this


process


to the energy


for electron


attachment


to the


free metal


ions


the coordinated


heterolytic

attachment


bond


ions


in solution.


enthalpies


to the complex


To obtain


a value of


change


the entropy


change


average M-O

for electron


required.


Estimates


of entropies


could


be obtained,


in principle,


determining the


temperature dependence of


the equilibrium constants


the gas-phase


FTICR


instrument


charge transfer


used


in this


reactions.


There


study to determine


s no provision

the temperature


on the


dependence of


was


used


ion-molecule


to attempt


phase electron


reactions.


Therefore,


to provide estimates of


attachment


to coordination


entropy


statistical


changes


compounds.


mechanics


gas-


results


of the


calculations


reported


in this


study


have


provided


insights


into


magnitudes

involving


of entropy

coordination


changes


complexes,


for electron


both


attachment


in the gas-phase


processes


in solution


have enabled estimates


to be made


for the change


in heterolytic M-O


bond


energies.


M(H20)

represent


Data


and M(H20)


one of


of this


ions,


type


are scarce


where M are


series


first


complex


for metal


transition


ions


complexes.


series metals,


for which metal-ligand


bond


energies


and solvation


energies


are known


for both


ions


that


form


the redox


couple.


Generally,


even


less


is known


of the


thermodynamics


of redox


processes


at metal


centers


involving negative


ions.


data


obtained


for the


B-diketonate


complexes


in the


present


work


therefore


broaden


present


understanding


of the thermodynamics


of redox


processes


that


occur


at transition metal


centers


in different


coordination


environments.












enthalpy of

uncertainty


the enolic O-H bond


since


no experimental


in acetylacetone


data


introduces


are available.


From


the greatest


results


of thermal

presented


gas-phase cha

in the present


enolic O-H bond


enthalpy.


rge-transfer


work,

From


reactions


an improved

the original


involving


estimate i

1 reaction


aca


s made


c' ions,

for the


calorimetry


data


improved


estimates


are made


for the average M-0O


homolytic


heterolytic


bond


dissociation


enthalpies


for M(acac)3


complexes.


data,


when


combined with


the gas-phase electron attachment


energy


data


for the M(acac)3


complexes,


has allowed


the average heterolytic


homolytic bond


dissociation


enthalpies


for the


corresponding


gas-phase


M(acac)3


" ions


to be determined.


It has been


shown for M(H20


redox


couples of


first


transition metal


series


ions


that


the trend


in the magnitudes


reduction


potentials


for these couples


can be related


quite


successfully


to the


trend


in the electron


attachment


energies of


free M+3


ions


(the negative value of


the third


ionization


potential


of M(g))


correcting the reduction


potentials


for the difference


between


heterolytic M-0


bond


enthalpies


in the oxidized and


reduced


form of


each


redox


couple.


35-37


Although


the difference


in absolute magnitudes


electron

solution


attachment

can only b


energies

e accouted


between M+3

for by adc


ions


in the gas-phase


litionally


considering


solvation


energies


, nephelauxetic


effects


in the


completed


ions


and the


absolute


potential

variance


neglected


of the electrochemical


of the


when


sums of


compared


reference electrode


these quantities

to the difference


is generally


used,


small


in heterolytic


bond


periodic


enough


to be


energies.


trend


energies


in the difference between metal


between


the ions


that


form redox


-ligand

couples


heterolytic


bond


can be estimated


from


3+/2+












line


for the electron attachment


energies of


free


ions.


In this


way,


a simple explanation


is provided


for the


trends


in the


reduction


potentials.

the M(acac)3


The trend


complexes


in the gas-phase electron


in the


present


work


attachment


energies


explained by using


similar


approach


to that


taken


for the M(H20) 32


couples.


Introduction


to Metal


B-Diketonate Complexes


transition metal


belong to


great


many


the general

B-diketone


class


ligands


complexes

of metal


that


investigated


in the


B-diketonates.5,39


coordinate


present


There


to metals.


work


are


general


structure


of B-diketones


is shown


in Figure


1-1.


The most


common


ligands


hydrogen,


have R1


and R2


but several


= alkyl,


other


perfluoroalkyl


ligands


have been


and aryl

reported


groups,


which


and R3


R3 is


also


alkyl


or aryl.


?R2

0


Keto


Form


Enol


Forms


Figure


1-1.


Structure of


B-diketones


in keto and


enol


forms.


Figure


1-1 illustrates


the the keto-enol


tautomerism


that


exists


in many


B-diketones.


hydrogen


atom at


the B


ring


carbon


atom


S. ^^
\ R, R
C
0
0


\ /

























































Ligand


Abbrev.


Acetylacetonate


acac


Trifluoroacetylacetonate

Hexafluoroacetylacetonate


tfac

hfac












(cisoid)


conformation.


The proportion


of the enol


tautomers


generally


increases when


an electron withdrawing


group


such


as a halogen


atom


present


as R3.


The enolization


also


increases when


ligands


fluorinated or


contain


an aromatic


ring.


Substitution by


a bulky


group


(e.g.


alkyl)


at the


ring a or


carbon


atoms


causes


steric


hindrance


between R3


and RI


particularly


in the enol


tautomer,


this


together with

significantly


the inductive effects of


reduce


the proportion of


the alkyl

the enol


groups may


tautomer


at equilibrium.


Since


complexation


to a metal


is believed


to occur through


enol


form


ligand,


result


poor


attempts

yields.


to obtain metal


complexes


of these


ligands


often


complexes


transition metal


investigated


complexes


in the


of the ligands


present


hfac,


work are


tfac


tris-chelate


acac.


structures


structure


of the


of the


coordinated


complexes


ligands are given


themselves


are


shown


in Figure

in Figure


, which


shows


the two optical


isomers


that


exist


in tris


B-diketonate


complexes.


are












Table


1-1.


Structural


Details


of Metal


Tris


(B-Diketonatesj


Complex

V(acac)


V(acac)3(

Cr(acac)3

Mn(acac)3

Fe(acac),


Co(acac)3


Co(acac


(Bu4N*


Average


O-M-O
Angle

88.0


87.3

91.1


97.2


87.1


97.3


91.5


c)
salt)


acac)3


Cr(hfac)3

Fe(hfac)3


94.0

87.0

87.0


Bite


M-O


Average
Bond


Length/A


.979


.982

.952

.901

.992'

.898

.981


.000

.987

.999


aData

bData

CData

dData

eData

Data

Data

hData

'Data


taken

taken

taken

taken

taken

taken

taken

taken


from ref

from ref

from ref

from ref

from ref

from ref

from ref

from ref


taken from ref


3(a)a












For symmetrical


two optical


isomers


ligands


are possible


and R2

(Figure


in Figure


1-3).


are


The d


and 1


same),


optical


isomers


of Cr(hfac)3


have been


isolatated by


gas-chromatographic


techniques


by using


an optically


active


support.


For unsymmetrical


ligands


can exist


and R2


in a


cis or


Figure

trans


are not the


conformation.


same)


each


It has been


optical


found


isomer


using


gas-chromatograph equipped with


an electron


capture dectector


that


Cr(hfac)3

gas-phase.


unsymmetrical

investigations

intramolecular


undergoes


dynamic


cis-trans


Tris(B-diketonate)


ligands


have


intramolecular


transition metal


received


of the mechanisms


structural


that


isomerism


considerable


have been


isomerism


complexes

attention


in the


regarding


proposed


in tris-chelate


complexes.


50-52


several

X-ray


are


of the


crystal


tris-chelate metal


structures or


available.


"bite"


complexes


gas-phase

angle of t


studied


electron


ligands


in this


diffraction


and the M-0O


report,

structures


bond


lengths


obtained


from these


investigations


are presented


in Table


1-1.


"bite"


angle of


the oxygen donor


atoms


is in all


cases


is quite


close


, which


gives


a pseudo-octahedral


arrangement


about


central metal


atom of


0 donor


atoms.


Properties


and Applications of


Metal


B-Diketonates


In this


section


some


background


is given


of the


chemical


physical


properties


and applications


transition metal


B-diketonates.


The emphasis


on the M(acac)3,


M(tfac)3


and M(hfac)3


complexes


of the


first


study,


transition metal


although other


series,


complexes


which


are the


are included.


subject


Much


of the


of the


present

relevant


* ~1 nL a a a A.. t. .7 --A S S -


i i


u.^


_ *












Rather,


this


section deals


with


the more


interesting


relevant


miscellaneous


literature on


transition metal


B-diketonates


that may


serve


to acquaint

The physical


reader with


and chemical


these


properties


compounds.


transition metal


B-diketonates


have generated


a great


deal


of research


interest


since


they were

compounds

properties


first


stems


synthesized


not only


as coordination


in the


year


from their


complexes,


1887.


spectroscopic


but also


from


interest


in these


structural


their


remarkable


physical


properties.


Many metal


B-diketonates


are volatile,


which


Morgan


and Moss


in the


year


1914


to describe B-diketones


as the


ligands


that


"gave wings


to metals"


The factors


that


determine


volatility

octahedral


of metal


complexes,


B-diketonates


an increasing


have


been


amount


discussed.


of fluorination


Generally,


in the


ligand


leads


to greater volatility.


Hence,


for the complexes


studied


in the


present


work,


the order


of increasing volatility


is M(acac)3


< M(tfac)3


< M(hfac)3.


The M(tfac)3


complexes


are usually


only marginally more


volatile


than M(acac)3 due


to the dipole moments


present


in the


cis and


trans


forms


of M(tfac)3


complexes.


volatility


of transition metal


B-diketonates


has enabled


them


to be


applied


studied by


a variety of


to ligated metal


centers


physical


that


methods


exist


that


as ions.


are not readily


vapor-phase


He(I)


photoelectron


spectra


of M(hfac)3


and M(acac)3


complexes


have


been reported.


54,55


The spectra


were


interpreted


in terms


of elementary


molecular


orbital


theory,


which


yielded


information


concerning the


details


of the metal-ligand


bonding,


and in the


case


of transition metal


comply


exes


, information about


the the relative energies of


the metal


ligand


orbitals.












method


does


not require


high


vacuum and


accordingly


has the


advantage of


relative ease


for large


scale


application


with


poss


ibility of


coating


complicated


shapes.


Thin


films of


superconducting


YBa2Cu307


have


been


prepared


a process


that


involves


thermal


decomposition


flow of


a vapor mixture of


B-diketonate


precursors of


, Cu and


Ba in


argon.


There


are several


comply


exes


of yttrium and


copper that


sufficiently


volatile


and thermally


stable


to be used


for this


purpose


These


include


Y(dpm)3


Cu(acac)


and Cu(dpm)


". Barium


complexes


are


less


thermally


stable


experimental


and decomposition has


conditions.


The most


been


success


reported


this


under


respect


the

has been


obtained


with


Ba(fod)2,


where


fod = 2,2


dimethyl-6,6,7


7,8,8,8-


heptafluoro


octadionate.


B-diketonate precursors


volatilized

controlled

the gas mix


in separate


to give


ture before


sources


the desired


it reaches


and their


flow rates


stoichiometric


a high


ratio.


temperature


are


carefully


Oxygen

reactor


is added


containing


substrate onto which


the superconducting


layer


to be deposited


Water vapor


has been


added


to the oxygen


flow to


aid in the decompostion


of the complexes


hydrolysis.


Substrates


used


so far have


been


rTiO3,


Al203


and yttria


stabilized


zircona


(YSZ),


deposited


films


are


usually


5-10


pm thick.


After the decomposition


period,


variety


of annealing processes


have been


used


(depending


on the


B-diketonate


precursors


used)


to convert


initially


deposited


layer


into


superconducting


YBa2Cu307.


By this method,


films


of good


compositional


and dimensional


uniformity


are produced.


A similar method


has been


type


used


These


to produce

thin-film


thin


superconducting


superconductors


films of


have critical


TI-Ba-Ca-Cu-0


temperatures


range


of 90-120


K with


the onset


zero


resistance


at 65-100


-. S .t a


are


are


I a












The volatility


of metal


1-diketonates


has allowed


several


investigations


of their


gas-phase


positive


and negative


ions


using


mass


spectrometry


Much


of the work with


positive


ions


has concerned


the determination


appearance


potentials62


and mechanisms


fragmentation


subsequent


interesting work has


to electron


been reported by


impact

Pierce


ionization


Some


and co-workersM


investigation


of the secondary


ion mass


spectrometry


(SIMS)


laser


desorption


of solid


samples


transition metal


B-diketonates.


of the


aims of


the study was


compare


the ionic


species


formed by


conventional


El ionization


to to


those


formed


from


SIMS


and LD.


SIMS


spectra revealed


catonization of


intact


neutral M(acac)3


complexes


ionic


fragments


produced


in the plasma,


as well


as the


ionic


fragments


themselves.


Ions


masses


corresponding to the


following


stoichiometries were observed M(acac) +


, M(acac)2


, M2(acac)3


M2 (acac) +. These


species


had also


been


observed


in a


study


of M(acac)3


complexes


using


high


pressure mass


spectrometry.65


Catonization


neutral

chloride


M(acac)3


of these


, Ag


cations


and NH4+


was also


were mixed with


found 1

Solid


to occur when


sample of


metal


diketonate.


SIMS


spectra


of mixed


samples


of M(acac)3


complexes


of two


different metals produced mixed metal


clusters


of the


same general


formula.


When


certain mixtures of


a metal


B-diketonate,


a chloride


different


transition metal


and a cationizing


agent


were vaporized,


ligand


exchange was


and NH4C1


found


produced


to occur.

Cr(acac)*


For example,


, Cr(acac)2


a mixture


SFe(acac) +


of Fe(acac)3,


CrCl3


, Fe(acac)2


acac)-CH3 ]


For other mixtures


no ligand


exchange


fragments


were


detected.


spectra


of laser


desorbed


samples


produced many


of the


same


fragment


ions


observed


in the


SIMS


experiments.


Interestingly,


rn a rr-nrao ni tho nroaoni -hfl1r-~ 1 4nnnd ovr'hnnrwo Ii a boon nhantvnd


* ---1-


S
nfl


1 < nan


h hoon


rnaoi~xror


&


LJI i r ar _


f-


T n












exchange was


found not


to occur.


To probe the


structure of


bimetallic


clusters,


Pierce


and co-workers


used


collisional


dissociation


to observe


pathways


for fragmentation.


The resulting


spectra


indicated


that


the cluster


ions


could


not be considered


simply


as metal


cations.


Rather,


a stable


structure


involving metal


atoms


was


invoked


with


possible metal-metal


bonding.


Reports


on the negative


ion mass


spectra


of metal


B-diketonate


complexes

volatility


have


focused


very


largely


large


cross


on M(hfac)

sections


complexes


for electron


due to their


high


capture.


thrust


of the work has


been


to determine


the fragmentation


pathways


the parent


ions


following


70 eV ElI


ionization.


66-71


possibility


using negative


ion mass


spectra


some metal


B-diketonates


as an


analytical


technique


in the field of


ultra


trace metal


analysis


has been


investigated.67


Some results of


previous


investigations


of negative


ions


formed


from metal


B-diketonate


precursors


are discussed


in the


experimental


section


this


dissertation,


in comparison


to the


results


obtained


in this


work.


A large number of


metal


tris(B-diketonate


complexes exhibit


reversible electrochemical


behavior,


especially those containing the


metals


Ru and


There


are numerous


reports


on the


effect


of the


ligand R


substituents


(Figure


1-2)


on experimentally


observed E1/2


values


for electrochemical


reduction


of these complexes


72-76.159-164


substituent


effects


are quite


pronounced.


For example,


values


reported


for Ru(dpm)


and Ru(hfac)3 differ


1.84


V in


dimethylformamide.


For series


of tris(B-diketonate)


complexes


of the


same metal,


the trends


in reduction


potentials


correlate


predictably


with


the electron


releasing or withdrawing


nature of


ligand


ring


aithal- 4 Fnort4- a 4-ho nrAor V.,; OOO .aaA..n. 4 an Ca.. n am 1 a.. an a LItt


- -


LJ


f~hl l o


*/-/4 /^+ /^.*"












aromatic"


character


It has been


shown


that


there


a strong


correlation between


the trends


values


for the reduction


series


of tris(B-diketonate)


complexes


of the same metal


and Hammett


parameters


that


have been


derived


from observations


of the effect


ring


substituents


on the


thermodynamics


and kinetics


involving


reactions


of organic


aromatic


compounds.


Interestingly,


for complexes


varying


with R3


= H (Figure


1-2),


there


is generally


a closer


correlation between El/2 potentials


a para


parameters


than meta


parameters


despite


the meta


position,


with respect


to the metal


center,


of the carbon atom that bears


the ring


substituent.


However,


since


oxygen


donor


atoms


in the


ligand


are para


to the


substituted


ring


carbon


atoms,


the phenomenon has


been attributed


to the distribution


electron density


values


at the oxygen


can be explained


atoms.


in terms


From this


of ligand


standpoint


field


value of


theory


considering the varying magnitude of


the spherical


component


of the


ligand


field


The

manifest


produced by the oxygen


quasi-aromatic


nature of


by the occurence of


donor


atoms.


coordinated B-diketonate


electrophillic


substitution


ligands


reactions


metal


B-diketonate complexes.


These


reactions


produce


complexes


that


are not


easily


formed by normal


reaction


routes.


Substitution


occurs


B carbon


electrophiles.

halogenation,

formylation.


atom of


The wide


nitration,


The reaction


ligand

variety


(Figure


1-1)


of reactions


diazotization,


conditions must


with


a variety


can be classified


thiocyanation,


be chosen


into


acetylation and


so that


acid


labile


B-diketonate


rings


are not


degraded.


The most


widely


studied


complexes


are therefore


ruthenium(III)


which are


those of


chromium(III)


not hydrolyzed


in acid


cobalt(III)

solution.


and R2












Description


of the FTICR


Technique


Production,


traopinQ,


and mass


analysis of


ions


In 1974


Marshall


and Comisarow77


developed


a method


of applying


Fourier transform technique


to the analysis


of the masses


relative


abundances of


ions


trapped


an ion cyclotron


cell.


simultaneous


detection of


many


ions


over


a wide mass


range


circumvented


many

mass


of the


limitations of


spectrometry


ICR)


the original


technique.


Since


scanning


then,


ion cyclotron resonance


Fourier


transform


method,


known


as Fourier transform


ion cyclotron


resonance mass


spectrometry


(FTICR)


has developed


into


a powerful


versatile


technique


in mass


spectrometry.


FTICR


technique


is based


on the


classical motion


of ions


described by elementary


laws


of electromagnetism.


The magnetic


force


(Lorentz


force,


= q(VxB)


acting


on a particle of


mass


M, charge q,


initial


velocity


V in


a field of magnetic


induction


B causes


follow


a helical


path


Figure


1-4.


The constrained


circular motion has


frequency

frequency


in Hz given by v


falls


in the


= qB/2irM.


range of


This


radio wave


frequency


is the cyclotron


frequencies


(0.01


- 2.00


MHz)


for magnetic


fields


on the order


of 1


tesla.


To prevent


ions


from


travelling


along the


helical


path


and being


lost


, ions


are


produced


between


two trapping


plates perpendicular


to the magnetic


field.


These


plates


are maintained


at a repulsive


potential


(typically


or -1 volt


for positive and negative


held


in a


defined


ions,


region between


respectively), a

the two plates.


ions


thereby


Excitation


sets


of plates


magnetic


and detection of


(transmit


field between


and receive


trapped

plates)


ions


lying

n tho


require


along the


additional


axis


of the


the tranoino nlateB.


are


heavl




proT



















electron
collector


receiver
plate


trapping
plate


transmitter


receiver


grplate


grid


filament


tra pping
plate












used


in the


present


study


has a 2


tesla


superconducting magnet).


Ions


can be


formed


the cell


from the


low background


pressure


admitted


sample by


an ioni


zing electron


beam


passing


through


small


holes


in the


trapping plates or


by photoioni


zation


via irradiation


through


semi-transparent


grids


one or more


plates


. Application


external


oscillating


electric


field


across


transmit


plates


at the


characteristic


cyclotron


frequency


an ion


causes


ions


of that


mass


cell


orbits of


to move


larger


into resonance with


radius.


The kinetic


the applied

energy of


field


spiral


ion is given by


= 27r2


into


2 2


where


resonance with


r is the radius


the applied


electric


of the orbit.


field


As the


their motion


ions move

is shifted


from having


a random distribution


simultaneously moving


phase with


of phases


to that


the applied


field


of all


as a "packet"


ions.


If the


applied


field


is turned


or moves


out of phase with


ions,


ion packet


persists


long enough


to induce


an image


current


the detect


plates80 before


collisions with


neutral


molecules


restore the


initial


cyclotron


random distribution


frequency


of phases


of the ion packet


induced


contains


image


information


current


in the


at the


time


domain


about


the frequency


(mass)


of the


ion,


inten


sity of


signal


produced


is dependent


on the


ion population.


In order to


simultaneously detect


the masses


populations


many


different


ions


present


in the cell


, a fast


radio


frequency


sweep


applied


to the transmit


plates


corresponding to


the mass


range of


interest.


As each


ion of


a particular mass


moves


into


resonance


superposition


signal

stored


of image


is amplified


a computer.


currents


digitized b

The rapid


is generated

y an analog


sweep/detect


in the detect


to digital


circuit.


converter


is repeated many times












a mass


spectrum.


magnitude of


The high mass


the magnetic


field


range

, with


ais determined


increasing


primarily


resolution


by the


toward


lower


masses.


tesla


field


yields good mass


resolution


up to approximately


3000


amu.


Thus,


FTICR technique


has the


high


resolution


at large


values


complexes.


required


to study many


The lower mass


limit


higher molecular weight metal

is governed by the maximum rate of


signal


digitization.


With


a 5.2 MHz digitizer


and a 3


tesla magnet,


this


limits


the detectable masses


to >17


amu.


A lower magnetic


field


allows


the detection of


accompanying decrease


important

high mass


lower mass


ions


such


as OH"


with


resolution.


Manipulations


of ions in the trao


Between


the ionization


and detection


events


any one


ionic


mass


be kinetically


excited by


application


a single


frequency pulse


transmit


plates.


A range


of masses


can be excited by


a frequency


sweep.

absorb


Selected


sufficient


ions


can be ejected


energy


to spiral


from


the cell


out to orbits


completely


of such


large


if they

radius


that


they


strike


the cell


plates


ion ejection).


a low amplitude


pulse or


sweep


is applied,


the kinetic


energy


ions


can be


increased without


ejecting them


from the cell


technique


can be


used


to explore endothermic


of reactants,


and this


reaction


translational


channels by

excitation


increasing the


one way


energy


by which


structural


and thermodynamic


information


can be obtained.


An important


factor


contributing to the great


versatility of


FTICR


is that


tailored


pulse


sequences


can be


applied


in almost


combination.


can

















CHAPTER


EXPERIMENTAL PROCEDURES


AND


RESULTS


Preparation of Tris(hexafluoroacetylacetonate)


Scandium and


Complexes


Qallium tris(hexafluoroacetvlacetonate)


aqueous


chloride,


solution


containing


an excess of


ammonia


approximately


solution


was


gram of

added,


scandium or


which


gallium


precipitated


Sc(OH)3 or Ga(OH)3


respectively.


The precipitate was


filtered,


washed


and dried and


then


refluxed


one hour with


a 3-fold molar


excess


hexafluoroacetylacetone


(20%


in light


petroleum ether).


When


cool,


reaction mixture was


filtered,


and the


filtrate evaporated


to yield


colorless


crystals


(Sc(hfac)3)


or pale orange


crystals


(Ga(hfac)3


crystals were

purification.


sublimed at


torr


and 40-50C to effect


further


Titanium and


vanadium tris(hexafluoroacetvlacetonatei.


Both


these


complexes

standard

manifold.


light

TiCl3


are air


techniques


sensitive


involving


A 3-fold molar


petroleum ether)


a Schlenk


tube


was


and preparation


Schlenk tubes


excess


added


against


was


achieved by using


and a Schlenk argon/vacuum


of hexafluoroacetylacetone


to approximately


a flow of


argon.


gram of


(20%


VCl3 or


The mixture was


refluxed


for three


hours


under


a blanket


argon


then


allowed


cool.


solvent


containing the


dissolved


product


was


decanted


from


any unreacted


solids


into


a second Schlenk


tube,


which


had been


purged


with


argon,


prior to the


transference


using


a cannula


with


filter


attachment.


solvent


was


removed


by vacuum


to yield


chocolate












Chromium


tris(hexafluoroacetylacetonate).


This


compound


available


commercially


from Strem Chemicals


Ltd,


was


used


received.


ManManese trislhexafluoroacetvlacetonate).


The most


convenient


and simple method


of preparation


for this


complex was


found


to be that


reported by


Evans


and co-workers.55


Approximately


gram of


Mn203


added


to a


Schlenk tube,


followed by


a 3-fold molar excess


hexafluoroacetylacetone


(20%


in light


petroleum ether).


The mixture was


refluxed


for 48 hours


under


an argon


atmosphere


then


allowed


cool.


The resulting


black


solution


was


filtered


concentrated


yield


dark


green


crystals,


which


were


purified by vacuum


sublimation.


Only moderate


yields


of Mn(hfac)3


are obtained by this method,


since


it is


simple


for the gas-phase


and convenient,


studies


and only milligram


reported


amounts were


in this dissertation,


required

procedure


adequate.


Cobalt


tris(hexafluoroacetvlacetonate).


The most


convenient


method


for the


preparation


of Co(hfac)3


was also


found


to be that


reported by


Evans.


To approximately


gram of


cobalt


trifluoride


(CoF3)

which


in a Schlenk tube was


in this


reaction acts


added


gram of


as a hydrogen


anhydrous


fluoride


sodium


scavenger.


fluoride,

A 6-fold


molar


excess


(to the


amount


of CoF3)


of cooled


hexafluoroacetylacetone


added slowly to


powder mixture and


then


reaction mixture was


refluxed


one


hour.


Note that


no solvent


is added


to the


reaction


mixture.


During the


reflux period


the solution


turned


deep green.


Approximately


20 cm3


of light


petroleum ether was


then


added


to the


reaction mixture


, which was


stirred


and then


filtered.


solution


concentrated


to yield


dark green


crystals


of Co(hfac)3,


which


were


was


was


was


was












Preparation of


Tris(acetvlacetonate)


Complexes


except


11 the M(acac)3

for Ti(acac)3.


sublimation.


complexes


were


purchased


The compounds were


The Ti(acac)3


complex,


it is necessary to exclude


like


atmospheric


(Strem


purified

Ti(hfac)3


oxygen


Chemicals


before


is air


from


use


Ltd.)


vacuum


sensitive,

reaction


mixture during preparation by using


Schlenk apparatus


as was


done


V(hfac


Ti(hfac)3.


The complex was


prepared by


slowly


adding


mixture of

solution o


grams


of acetylacetone


f approximately


gram of


and 2

TiCl3


grams of

stirring


triethylamine


in 25 cm3


to a


of ethanol,


under an

addition


argon


atmosphere


and refluxing


accompanied by


reaction mixture


is not


a dark blue


necessary.


coloration


Formation


in the


becomes


of the


solution.


hot during the


complex


After


stirring


for 1


hour the


solution


containing the dissolved


product


was


transferred


to a second Schlenk tube


that


had been


purged with


argon.


solvent


removed by vacuum to


yield


dark blue crystals of


Ti(acac)3.


Purification was


ethanol/water mixtures

sublimation before use


Preparation


effected by repeated recrystallization


The product


was


of Ruthenium


from degassed


further purified by vacuum


Tris(B-diketonates)


ruthenium B-diketonate


complexes


investigated


in the


present


work


are


Ru(hfac)3,


Ru(tfac)3


and Ru(acac)3


complex


hfac)3


available


from Strem Chemicals


Ltd and was


used


as received.


The other


two complexes

reported by E


were


ndo


prepared by


and co-workers.


using the


rutheniumm blue"


Approximately


grams


method

of hydrated


-7


was












this


time


initial


orange


color of


solution


became


almost


black.


A 9-fold molar


excess


of ligand


(trifluoroacetylacetone or


acetylacetone)


was


added


to the


reaction mixture which


was


then


allowed


to continue


refluxing


for an additional


hour,


during which


time


solution became


red.


Next,


12 grams of


potassium hydrogen


carbonate


dissolved


in 50 cm"3


de-ionized water was


added


to the


flask


dropwise


over


a period


of 10 hours


while the


reaction mixture was


continued


to be


refluxed.


flask was


cooled


and the


solvent


was


evaporated by using


a rotary evaporator.


Benzene was


added


to the


flask


to dissolve


residue,


which


was


then


washed


with


three


portions


of 1 M


sodium hydroxide


solution.


The washed benzene


solution


was


dried


standing


over


purified by


anhydrous


sodium


loading onto a


1/2"


sulfate.


Finally,


chromatography


column


product

packed


was


with


mesh


alumina.


The column


was eluted with benzene


resulting


solution

crystals


concentrated

(Ru(tfac)3).


to yield or

No further


ange crystals

purification


(Ru(acac)3)


or red/orange


of these compounds


was


found


to be necessary.


OrQanic


Compounds


The organic


compounds


employed


in the


present


study were


purchased


from


commercial


sources


and used


without


further


purification.


extraneous or


fragment


ions were detected


in their


negative


ion mass


spectra.


Electron Attachment


Studies


J i D L m












dependence of


populations


of parent


negative


ions


formed


from a


mixture of


known


partial


pressures


of two


reactants


are monitored


they


charge


transfer with


the neutrals.


For the reactions


indicated


2-1,


free energy


involved


for electron


capture


species


be bracketed


within


the lower


limit


of the


known


value


for A and


upper


limit


of the


known


value


+ B


+ C


+ B"


+ C


When


the free energy


change


is small


kcal


with FTICR)


as in the case


, the equilibrium populations


the ions


can be measured.


+ B"


neutral


reactants


are in large


excess


and their partial


pressures


not vary during the


reaction


The equilibrium constant


for the


reaction


in equation 2-2


can be obtained


from the ratio of


the equilibrium


population


reactant


spectrometer


calibrated


of the two ions,


gasses.


and the ratio of


Measurement


is achieved by using


for each reactant


the partial


pressures


an ion


by using


gauge.


an external


pressures


on the mass


gauge was


baratron


capacitance manometer


in the


pressure


range of


torr.


- 10-5


Special


pressure


calibration


procedures


developed


for the FTICR


systems were


used


that


ensure


uniform reactant


gas pressure throughout


system by


adjusting the


relative


pumping


rates of


the two diffusion


pumps


connected


to the


high


vacuum


chamber.83


The equilibrium


constant


a a a S S


can


I I


m


A


*












charge-transfer


equilibrium method has


been


used


in ICR


experiments16-19


and PHPMS experiments10d15


to provide electron


attachment


energies

organic

enthalpy


for a large

compounds st


change


number


died,


(AHrxno)


of organic


compounds.


the corresponding


have been obtained by


entropy


For many of


change


following the


temperature


dependence of


the equilibrium.


11,12,14,15


The results


have


produced


ladders


of multiple overlapping values


AGrxn'


AHrxn


and AS


pairs


of organic


reactants


such as


substituted benzophenones,


nitrobenzenes,


10,11,13,17-19


quinones14,19


and dicarbonyls.


absolute


values


for electron


capture


by each


compound,


(defined by


AGa


for the


reaction A


= A')


are obtained by


including


an external


standard


in the


ladders


for which AHa


and AS


are well


established.


For example


EA of


SO2 has


been accurately determined


to be 1.097


0.036 eVM


and 1.107


photoelectron


0.0008 eV85


spectroscopy of


in two

SO2",


independent


ind SO?


investigations


is the reference


compound


chosen


in the EA


investigations


of Kebarle.


value


evaluated by the methods of


statistical mechanics


from


structural


and spectroscopic


data.


Electron attachment


and electron


transfer


ecuilibrium


studies


using the


Nicolet


FT/MS


1000.


Gas-phase


charge-transfer


reactions


type outlined


2-1 and in


were


studied


in the


present


work by using


a Nicolet


FT/MS


1000


Fourier


transform


ion cyclotron


resonance mass


spectrometer


(FTICR


A diagram of


instrument


used


given


in Figure


2-1.


The technique used


in the


present


work was


similar to


that


reported


previously


in ion cyclotron resonance mass


spectrometry


(ICR)


investigations.


and pulsed high

e temperature of


pressure


mass


the reaction


spectrometry


cell


(PHPMS)


was measured


under


was



































Ion Gauge


Superconducting Magnet
II

SSorxjs Prb
* I


Inlet System


-. -- ..-.-..--- .-.--.-..- ..


Ion Trap

Gate Valve Baratron




Mechanical Pumps


Diffusion Pump


Inlet Diffusion Pump












measured


equilibrium constant,


and a value of


for the


organic


compound

compound

organic

to admit


at the reaction


from the


compounds


tabulated


temperature


values of


and the M(hfac)3


into the mass


spectrometer


of 350 K (obtained


and AS ).


complexes


through


were


for each


Most


organic


of the


sufficiently volatile


leak valves


without


heating.


Less


volatile organic


and the M(acac)3


complexes


were


sublimed


tip of


a solids


temperature of


probe


- 350 K.


placed well


Negative


away
ions


from the


were


ion trap,


produced


which


was


from neutrals


FTICR


capture by


trap by


the metal


capture of


low energy


complexes was,


electrons


in most


cases,


Electron


accompanied


varying


amounts


of fragmentation.


Parent


ions were


selected


from


these


fragments


ion ejection


techniques.


To approach


collisional


thermalization


ions


prior


to the


ion/molecule


reaction,


FTICR relies on a


set thermalization


period


between


pressures


ionization


in this


and detection


study were


of product


in the 10"6 torr


ions.


range,


Typical


reaction


but a bath


such


as argon


or cyclohexane


can be


added


to reactant mixtures


if lower


reactant


pressures


are used.


For both bracketing


and equilibrium


experiments


a thermalization


period


of 1


s was


used


Assuming


a second


order


collision rate constant


pressure of


10o6 torr,


each


molecule"1


ion collides


sec


an average of


about


at a total

it 30 times


with


neutral


reactant


molecules


before


charge-transfer


reactions


were


followed.

populations


When


a charge-transfer equilibrium was observed,


were determined by measuring the


relative


abundance of


parent


ions over


suitable


time


intervals


until


they


reached


constant


value.


The equilibration


could


be followed


for long


reaction


times


" 20


s) ensuring


complete


thermalization.


At the


reactant












equilibrium.


The electron


attachment


energies


for all the


compounds


studied


are presented


in Table


2-1.


results


are also presented


Figure

in the


2-2 to illustrate


present


the organic


reference compounds


that


were


used


work.


Table
for M(


2-1.


acac)


Free


Energies


of Electron Attachment


3, M(tfac)3 and M(hfac)3


Complexes.


(kcal


mol'-)


at 350 K


Sc(hfac)3


hfac)3


V(hfac)3

Cr(hfac)3

Mn(hfac)3

Fe(hfac)3

Co(hfac)3

Ga(hfac)3

Ru(hfac)3

Ru(tfac),


-64 3c


-69 3c

-73 2b


Sc(acac)3

Ti(acac)3

V(acac)3

Cr(acac),


-67 3c


-109


-93)


(-97)a

-60.4

(-89)a

-64.0 b


Mn(acac)


a Fe(acac)


Co(acac)


0.5b


-24.9


-20 1c

-59 3c


-43.0


0.5b


-47 2c


Ga(acac)


Ru(acac)


-38.7


0.5b


t 0.5b


aEstimated


value


values


for M(acac)3


obtained by


complex


adding


50 kcal


mol-1


to corresponding


(see text


bValue obtained from
Reference compounds


measured equilibrium constant.


given


in Figure


CValue


obtained by


bracketing


(see eq


2-1).












.--Mn(hfac)3 (109)


-*Co(hfac)3 (97)
Fe(hfac)3 (93)

Ru(hfac)3 (89)


Chlorine atom 83.4


CN
C
CN


V(hfac)3


73 4


Ti(hfac)3 69


Ru(tfac) 64.0


Cr(hfac)3 67

Sc(hfac)3 64


F F


Ga(hfac)3 60.1
Mn(acac)3 59


-56.0-


Co(acac)3 47


- 45.3


Fe(acac)3 43.0


NO2-6 CN -- 38


.8 -


26.3-


Ru(acac)3 38.7


V(acac)3


- 21.3--


Cr(acac


CH3 CH3


19.5-


48.7- -


42.7 --


CN
= CS












Electron


attachment


enerav


acac"


radical.


electron


attachment


energy


of acetylacetonate


radical


was


determined by the


bracketing method,


in which


occurrence or non-occurrence


of charge


transfer


reactions


involving


acac


- ions


with


organic


reference


compounds


were observed


2-1).


acac


" ions were generated by


heating


Co(acac)3

pressure


tip of


(-10"7


torr)


a solids


of Co(acac)3


probe


in the


to produce


FTICR main


a low partial


chamber.


Acetylacetonate


anions


were


produced


following


electron


impact


ionization


of the gas.


following the


time dependence of


population


acac


- ions


in the


presence of


approximately


torr


each


a series


of organic


reference compounds,


it was determined


that


acac


charge-transferred to


2,6-dichlorobenzoquinone,


tetrafluorobenzoquinone,


which


sets


limits


of the electron


attachment


energy


at 59 3


kcal mol"


(see


Figure


2-2).


Consistency


of Electron Attachment


Energy Determinations.


Although


lower


operating pressures


of ICR and FTICR,


compared


to PHPMS,


enable


low volatility


compounds


to be studied,6


this


also


introduces


greater uncertainty


in the measurement


of reactant


pressures.


To check


consistency


of the


results obtained


in the


present


work with


those


of previous determinations,


AGrxn


for the reaction


= 1,4-


dicyanoben


zene;


= 3-fluoronitrobenzene was measured.


For this


reaction


at 423 K Kebarle


has found


AGmrxn


= -3.2


kcal


cal mol


FTICR at


giving


a value


350 K we obtained


AGrxn


of AHrxn'

= -2.8


of -2.1 kcal mol"1


kcal


mol-1


which


In the


together with


the previous


determined entropy


change gives


AHrxn = -1.9 kcal


The discrepancy

temperature of


of 0.2 kcal


mol


the neutral


probably


error


arises


from


in measuring


uncertain


equilibrium


ann n A. -a J-I--~ --a -, --- A--- A- ~- 1 2.....2A. -r -3-,-~-- A a- -


not


mol


A


I i L


A-, 1l-












estimate of


the expected error


for free


energies


determined


equilibrium reactions,


and conservative


uncertainties


of 0.5 kcal


mol-1


assigned


to values


of AG
a


determined by equilibrium to


account


experimental

uncertainties


uncertainties,


in the assigned


including


temperature,


pressure


thermodynamic quantities


for most


of the


reference


compounds.


Electron


attachment


to tris (hexafluoroacetvlacetonate)


complexes


The M(hfac


complexes


studied


in this


investigation


were


those of


first


row transition metals


from Sc-Co,


Ga and Ru.


These


complexes


particularly volatile


and are easily


admitted


into


FTICR through


leak


valves on


inlet


system.


It has been


shown


previously70',71


that


for a series of

fragmentation f


first


row transition metal


following electron


capture


M(hfac)3


increases


complexes


from


that


left-to-right


row.


same general


trend


was observed


in the


FTICR


in this


work.


The major pathway to


fragmentation


was loss of


a ligand


ion,


this


ion predominated


in the mass


spectra


Fe and Co complexes


immediately


after


electron


capture.


A few hundred milliseconds


after


ionization,


the parent


was formed by


charge


transfer


to the


neutral


complex


from the


fragment


ions.


After


a suitable


period


time,


any remaining

By observing


fragment


ions


charge-transfer


were ejected


reactions


from the


cell.


involving M(hfac)3


complexes


organic


reference


compounds,


was


found


that


few had


-AG values


complexes

reported.

Fe(hfac)3,


that


as high

d values


as that


of the complexes.


greater than


Although AG a values


Co(hfac)3


the order of


any of the organic


could


and Mn(hfac)3

a AG values


Co and Mn


compounds


so far


not be experimentally measured


estimates


runs


parallel


were obtained by noting


to the


series


are


are












was observed


which


of the two parent


negative


ions


predominated


after


a charge

complexes


transfer period.

was determined.


relative order


The difference


for the


in AG values


series


between


V(acac)3

results


and V(hfac)3


of two


was determined


to be


-50 kcal


separate equilibrium reactions.


mol"'1


Assuming


from the


a constant


difference of


50 kcal mol1


the other metals


between

series,


the M(acac)3

estimates coi


and M(hfac)3


uld be made


complexes


for the


M(hfac)3


complexes


= Ru, Fe, Co, Mn)


since


those


for the M(acac)3


complexes of

in this way


same metals were measurable.


have been


in parentheses


Values


of AG


obtained


in Table


substance with


chlorine


atom,


the highest


Cl-(g)


accurately


was included


known


electron


in the


study


affinity

of charge


transfer


reactions


with


the metal


complexes.


Electron


capture by


background


pressure of


Fe(hfac)3


with a


small


partial


pressure


of benzyl


chloride


produced


complex.


was


Cl (g

found


in addition


that


when all


to the ions


ions


except


formed


from


chloride were


the metal


ejected


from the cell


and its subsequent


reaction


with Fe(hfac)3


was


followed,


chloride


ion regenerated Fe(hfac)3


" by


charge transfer,


indicating that


the electron


attachment


energy


of Fe(hfac)3


> 83.4


kcal mol"1


accord


with


value estimated


above.


Charge


transfer occurred


from tetrachlorobenzoquinone


(C14BQ)


Cr(hfac)3,


an equilibrium reaction


was


not observed


in the


reaction


with


Sc(hfac)3


as the reaction


was


hampered


rapid


formation


of adduct


ions


(hfac)3.Cl4BQ]


Sc(hfac)3]2


Electron


attachment


to tris(acetylacetonate)


complexes.


M(acac)3


complexes


has been


were


studied


previous


for the series


noted


that


of metals


cross-section


Sc-Co,


Ga and Ru.


for electron


capture by


U


$4 ref ar., 4- -a ^ ne 4 4- 4 an mns4- n 1


r'^


^" ^IaVTi


I












substituents


in the


former.


The same general


effect


was


observed


this


report


for the complexes of


the metals


Cr to Co


The only


produced


from


ionization


of the


neutral


with


the electron beam was


ligand

charge


anion,


transfer


but unlike


the M(hfac)3


to the neutral


complexes


complex to


form


, the


ligand


the parent


ion did


-on.


Parent


negative


ions


of these complexes


could only


be obtained


in reasonable


yields

electro


following ch

n attachment


emical

energy


ionization by an

. In performing


organic


compound


experiments


with


of lower

these


compounds,

of ligand

detectable


therefore,


anion


from


fragment


was necessary to


the cell.


ions


The Ti


and had large


eject


relatively


and V complexes


cross


sections,


large


amounts


produced


in accord with


trends


in stability of


the ions


noted above.


The difference


in the electron


withdrawing


effect


between


in the


series


of complexes was


also observed


to markedly


reduce


values


of AG


for the M(acac)3


series


relative


to the M(hfac)3


series,


and the values


of AG


fall


well


within


range of


those


the organic


compounds


in the reported


electron


transfer


free energy


ladder,


which


extends


from


approximately


10-75 kcal mol1


This


enabled


bracketing


and equilibrium reactions


2-1 and


2-2 to be


followed


for the entire


series


of M(acac)3


complexes.


The Cr(acac)3


ion, although


initially produced


in the FTICR


cell,


was


unstable


underwent


rapid


loss of


ligand


a rate


that


increased with


total


pressure of


dissociation.

previously. 8


the system,

instability


Bracketing this


indicating


a collisionally


of the Cr(acac)3


compound


through


has been


induced

observed


charge-transfer


reactions


was therefore hampered by


competitive


ligand


loss,


produce


greater uncertainty


in the


result.


Parent


negative


ions


could












A value of


In contrast


for the


to all the other


Ti(acac)3

complexes


complex

studied,


could


not be obtained.


Ti(acac)3


or its anion


did not


undergo detectable


electron


exchange


in the


time


scale


obtainable with


the FTICR,


even


with


relatively


high


pressures


neutral


gas.


Exothermic


charge


transfer


reactions


involving


Ti(acac)3


with

10"4)


various c

over the


)rganic rE

range of


sactants were too


to 1


slow to


eV of driving


follow


force


(krxn/kco


llision


The cause of


this


unexpectedly


slow ga


s-phase


charge transfer


not known


and would not


have


been


predicted


for a dl/d2


redox


process.


Charge-transfer


equilibria


were observed


for the


V and


complexes


, and results


for Cr


Mn and Co were obtained by the


bracketing


technique outlined


Gas-Phase


Spectroohotometrv


of Cr(hfac)3


gas-phase


visible


spectrum of


Cr(hfac)3


was


determined


order


to compare the


spectrum to


that


of Cr(hfac)3


in solution


(see


chapter

designed


The ga


sample


cell


s-phase


with


spectrum was


10 cm path


obtained by using


length


and fitted


with


a specially


heated


quartz


windows


a temperature


and separately


a few degrees


heated


cell


cooler than


body.

that


The body was maintained


cell


windows


ensure


that


crystals


of Cr(hfac)3


did not form on


windows


render


them opaque.


Crystals of


Cr(hfac)3


were


added


to the


cell,


which


then


evacuated and


positioned


in the


cell


compartment


an IBM


UV/visible


9430


spectrophotometer.


The cell


was gradually


heated


about


C to


produce


a practical


concentration of


vapor.


was

















CHAPTER 3


TERMINOLOGY


AND CONVENTIONS


USED


IN GAS-PHASE


ION THERMOCHEMISTRY


Introduction


Values


for the energy


required


remove


an electron


from


isolated


atom,


molecule or


ion are often


obtained by using


spectroscopic


methods


that


yield


the minimum energy


required


for this


process.


This


energy


is the


adiabatic


ionization


potential


(alP)


for neutral


positively


charged


species


and the electron


affinity


for anionic


species.


used


Mass


spectrometric methods


to estimate values


for electron


and other techniques


attachment


energies


have


also been


ionization


energies


at T


K as well


for T > 0


In combination


with


other


thermochemical


data,


alP


and EA


values


provide


fundamental


information


concerning


the thermochemistry


of ionic


processes


such


as charge-


transfer


reactions


and ion solvation.


For example,


extensive


compilations


of enthalpies of


formation


of ions


at 298


K (AHf)


derived


from


spectroscopic


and mass


spectrometric


data


are


available.


Tabulated


values


for AHf


of ions


depend


on the


convention


used


to treat


the gas-phase electron.


consistently to avoid


90e,91


errors


Therefore,

in derived


a convention must


data.


be used


convention,


thermal


electron


convention


TEC),


is widely used by


thermodynamicists


treats


the electron


as a classical


ideal


gas.


stationary


electron


convention


(SEC)


"ion


convention"


is more


commonly used by


mass


spectrometrists


and treats


the electron


as a subatomic


particle


Presented


here


are definitions


some


important


terms


frequently












use.


stationary


electron


convention


is adopted


throughout


present


work,


the free energies


of electron


attachment


to the metal


complexes


obtained


in the present


work


conform to


this


convention.


Since a discussion of

energies of electron


the stationary


attachment


electron


and ionization


convention

processes


applied


to free


apparently


not appeared


in the


literature,


a discu


ssion


is give


here.


Electron Affinities


and Adiabatic


Ionization


Potentials


The electron detachment


process


for a monoatomic


or polyatomic


species Mn"

positive or


shown


(where


n is


charge


zero


negative).


M"(g)


= M(g)


The enthalpy


change


for electron


detachment


can be


expressed


as the


sum of


the enthalpy


change at


K and


the difference


heat


contents of


the products


and reactants


at temperature


T, given by


difference


in the


integrated heat


capacities


over


range


KtoT


3-2).


AHo(Mn..Mfnll)


T T
- AEo..o+ fCp(Mn+1) dT+ Cp
0 0


term AE00


is the energy


required


to form M"1


in its ground


electronic,


rotational,


and vibrational


states


from M"


in its ground


state.


When M"


a negative


ion,


AE0-0


defines


the electron


affinity


When Mn


is a neutral


or positively


charged


species,


can


- Cp(M0
0


of M"


AH(M" n M"n












If the geometries


of Mn


and M"1


differ,


will


be formed


excited


state


and the energy


required


for the


vertic


processes


be greater


than


for the


adiabatic


cess


Stationary


and Thermal


Electron


Conventions


Usually,


though


not always,


Mn and M"n


are


chemically


similar

neglect


and the difference

d with respect to


in their


that


integrated


of the electron.


heat

The


capacitie

thermal


can be


electron


convention,


however treats


the electron


as an ideal


which has


while


an integrated heat


under the stationary


electron


set to


zero.


capacity


electron


at constant


convention


pressure of


heat


relationship between


5RT/


capacity of

enthalpies o


electron


detachment between


two conventions


is given


AH(TEC)


- AH(SEC)


= 5RT/2


free energy


change


for the


process


eq 3-1 at a temperature


be written


in terms of


assoc


iated


enthalpy


entropy


changes


3-4).


AG(Mn


=- AH0Mn


- TASo(M"


-* Mn+')


value of


n in


3-4 for free


energy values derived


from


experimental


charge-transfer


The total


ASo M


entropy


is equal


to products


equilibrium


change


studies10-19,92


for the electron


- Sreactants


limited


detachment


+ S


to 0


process
(Mn+1f) -


can


- Mn+1


Mn+


SM +












Since the masses


of MI1


and Mn only


differ


the mass


an electron,


strains


for Mn1


and Mn will


be virtually


identical


these


terms


3-5 will


essentially


cancel.


eq 3-1 AStrans


is therefore


negligibly


different


from


tra 0
trans


(e-).


The translational


entropy


an ideal


particles


mass m can be


predicted


from


statistical


mechanics


by the


Sackur-Tetrode equation93


(eq 3-6)


where


V is the volume of


gas,


is the


Boltzmann


constant,


L is Avagadro


s constant


is Planck's


constant


the temperature.


5 +i (2inmkT
2 \ h2}


term A


given by


eq 3-7,


where QeLec


is the electronic


partition


function.


ASetec


= R In (Qeec(products)/QeLec(reactants))


The electron has


an electronic


degeneracy


of 2,


can


therefore


be rewritten


as eq


3-8.


ASelec


= R in (Qelec(M


/QeLec(Mn)


+ R ln2


free energy


for electron detachment given


3-2 can now be


given


according


to the two conventions.


thermal


electron


convention


includes


terms


for the


electron


, and AG


for electron


achment


is given by


Although t
experiment


Sackur-Tetrode equation


and theory


gives


for the translational


good agreement


entropy


. .


between


an atomic or .


0
Straw














AGo(TEC)


- AEo.o+ cCp(Mn1
0


T
- Cp(M)dT+ -RT
0


- T(ASrot


+ vib


+ R ln(Qeec (Ml1)/Qe ec(Mn


+ Strans(e


+ R In 2)


stationary


electron


convention


neglects


all terms


for the


electron


and AG


electron


detachment


given by eq


3-10.


AG(SEC)


- AEo.o+fCp(Mn1) dT
0


-JCp(Mn) dT
0


ASrot


+ ASvib


+ R in(Qelec(M


/Qet (Mn


3-10


temperature


at which


two conventions


give


same


value


AG(Mn -4 Mn+1


any spe


cies


can be


found by


subtracting the


right


side of


3-10


from


the right


side of


3-9 and


setting the difference


equal


zero


(eq 3-11).


5RT/2


- T(Strans


+ R In 2


3-11


Coll


ecting


the constant


terms


from the


Sackur-Tetrode equation


gives


diff


erence


between AG values


for each


convention


temperature,


-12).


[(AG(TEC)


- AG(SEC)]/J


= T(118


.3145


ln(T)5/2)


3-12


At 0


, AG


of electron detachment


is equal


to the


alP or


EA values,


there is no difference between the two


conventions


However


3-11


also


eaual


at 296.96


zero


and the two conventions


nive


identical


- T(


sw


A.












this


system the


heat


capacity terms


for H atom and


ion cancel,


ASrot


are equal


zero.


intersection


of the


lines


occurs


at 296.96


K where


the two conventions


give


same


value.


values


for each


convention


at 298 K are within


-0.02


kJ mol1


so can


be assumed


to be approximately


equal


at this


commonly


used


standard


temperature.


significance of


the result


for the


hydrogen


atom


can be


seen


in calculations


hydrogen


electrode


of the absolute


94.95


given


thermodynamic


by the


standard


potential c

free energy


standard


change


H (aq)


e (g)


= 1/2


3-13


value of


for eq


3-13


can be expressed


as the


sum of


values


for three


elementary


steps,


94,95


one of which


involves


ioni


nation


a gaseous


hydrogen atom,


eq 3-14.


H-(g


= H+(g


e (g)


3-14


value


for this


process,


and hence


value


for the


absolute


electrode


potential


(or "single


ectrode


potential")94,95,96-98


depends


ultimately on


which


electron


convention


is used.


absolute


value of


standard hydrogen electrode


used


to obtain


absolute


electron


attachment


to molecules


solution.


As noted


above,


coincidence there


is virtually no difference between


conventions


at 298 K (absolute

comparison between


= 4.44


data


This


allows


for free energies


for example


of electron


direct


attachment


to gas-
t












Also


process

to allow


shown


in Figure


appropriate

calculation


3-1 (b)


spectroscopic


a plot


data


of the relevant


of AG


is available9-101


heat


capacities,


for I2+
for 12


For this


0o
rot


The obvious


difference between


the plots of


for the


ionization


of H


atom and


is that


slope


for the


ion convention


values


opposite

and M I


of H


Under


the ion convention


is considered


results in


the SEC)


For I


a loss


a 211


and so ASOeec

of electronic


state


is formed


only the electronic


never


equal


degeneracy


from


a 'g


degeneracy


zero.


ASelec'
state,


Ionization


= R In 1/2

and ASetec


In 3


in the


SEC.


For most


small


molecules


such


as I


TAS


term


aris


from a


difference


change


between


in electronic


the alP of


degeneracy will


a polyatomic molecule


produce

and AG


largest


ionization


at T > 0


K. The difference


in the


integrated


heat


capacities


of I


differ


only


0.09


kJ mol


at 298 K and


combined


values


of TAS


only


amounts to


-0.5


kJ mol


at 298 K


somewhat


smaller than


the contribution


from


TASelec


. Further,


enthalpy


capacities


these


change


will


will


terms


arising

always

cancel


from


have


in the


the change


same


final


sign


in the


integrated


as the entropy


expression.


heat


change


The predominance of


the AS


eco0
etec


term produces the almost


linear


change


in free energy


SEC)


with


temperature


as shown


in Figure


Exactly


analogous


plots


of AG


of electron


attachment


an ion


neutral molecule under the


two electron


conventions


can be obtained by


plotting the


negative of


electron


detachment


values


given


3-10.


of electron


capture


has been


calculated


Chowdhury


combined wit


and co-workers11


spectroscopic


at 423 K from


and theoretical


the electron


data


affinity&


for the


of SO2


geometries


and


are


of Mn












The electronic degeneracy


change


is dominant


in the stationary


electron


convention,


and the dependence


of AG(SEC)


on T deviates


only


slightly


from


linearity


over


the temperature


range


shown.









13.68

13.66

13.64

13.62

13.60


13.58

13.56

13.54


a
297 K
i SEC
I


>Adiabatic
ionization
potential


9.24-

9.22 -

9.20 -

9.18 Adiabatic
ionization
9.16 potential

9.14-

9.12 -

9.10 -

9 .0 8 ,, ,, ,,,,,,,,,,,,,,,,1 11 11 11 11


* | *I | I I* S | I uI*'| I I I I *U *JI I...s|


TEC


O


C
LU
Ld
(U




















-1.04

-1.06

-1.08

-1.10

-1.12

-1.14

-1.16


TEC


-(EA


297


SEC


-1.18


0 100 200 300 400
Temperature/K


500


600

















CHAPTER


INTRAMOLECULAR ENTROPY


COUPLES


CHANGES


FO


INVOLVING COMPLEX METAL


R REDOX
IONS


Introduction


Entropy


changes


that


occur


for electron


attachment


to gas-phase


polyatomic molecules (ASa

temperature dependence of


have been


equilibrium


obtained by


constants


determining the


for gas-phase


charge-


transfer


reactions


eq 2-1)


by the


procedures


described


chapter


The entropy change


is obtained


from a


Van't


Hoff


plot


of the


data.


types


of compounds


studied


to date


have been


predominantly


organic


compounds with


delocalized


t systems,


often


containing electron


withdrawing substituents.


typically


fall


For these


in the range of


compounds,

4 cal mol1


values


of ASa0
a


are


small


An important


consequence of


equal

values


this


and constant


result


over


for the organic


is that


a wide


compounds


range of


that


and AHao values

temperatures.


have


been


studied,


are approximately


In fact,


which


are


usually measured


at temperatures


above


300 K, are typically within


kcal mol


of their


values


at 0


that


their


electron affinities


The electron


attachment


energy


data may therefore be combined with


other


compiled

without


enthalpy or

introducing


free energy data


serious


at 298 K or


at other


temperatures


errors.


It is useful


to obtain


data


for the temperature


dependence of


gas-


phase charge-transfer


reactions


involving


organometallic


coordination


compounds


since


a more


complete


understanding


of the












variety


of calorimetric


thermochemical


data


for metal-containing


compounds

difficult


energy


cycles


to obtain by more


that


provide


thermodynamic


conventional methods.


data


Examples


that


are


of the


application


of gas-phase electron


attachment


energies


energy


cycles


are given


in chapter


Organometallic


coordination


compounds


are chemically


dissimilar


to the


types of


organic


compounds


that


have been


studied


it can not


be assumed


that


values


for these


types


of compounds will


also


small


in all


cases.


Temperature dependent


gas-phase charge-transfer


equilibrium

n4-butadiene


studies


iron


involving metal


tricarbonyl


AS has


containing


been


compounds


quoted


are


rare.


to be 10 3


mol-1


considerably


higher


than


typical


values


found


for the


organic


compounds


that


have been


studied.


In principle


similar


data


could be obtained


from FTICR studies


some means


were


available


control


temperature of


the reaction


cell


and main


chamber


(Figure


2-1).


Unfortunately,


in the determination


of AG
a


for the metal


complexes


reported here,


such a


facility was


not available


and entropy


changes


could not


be measured.


Despite


the general


lack of


experimental


data


for gas-phase electron


attachment


entropies


for coordination


complexes,


data


are


available


from


other


sources.


Estimates


for certain


couples


can be obtained


from


statistical


thermodynamics


calculations


when


there are


sufficient


structural


vibrational


data.


example,


Lowenschuss


and Marcus102


have


used


statistical


mechanics


calculations


to calculate


standard gas-phase entropies


large


number of


polyatomic


ions,


including the members


of the


redox












couples


IrC63-"2/


Another


source of


data


for entropy


changes


involving


reduction


of metal


complexes


electrochemical


changes


from


values


for half-cell


redox


studies

by using

couples


of the temperature d

Scyclic voltammetry.


involving


several


ependence of

Entropy


octahedral


tris


chelate


complexes


have been


obtained


in the


laboratories


of Weaver


and co-workers,


103-105


These


studies


have


been


primarily


concerned


with


relationship between


the rate of


electron


transfer


processes


between


metal


centers


to the overall


in solution and


driving


force of


the enthalpic


reaction.


entropic

Entropy


contributions


changes


redox


half-cells


consistent


with


(ASrc0)

the sta


obtained


by the cyclic voltammetry method


tionary electron


convention


are


for dealing with


entropies

electron


of electron attachment


in the reduction originates


to gas-phase molecules,


from


the electrode


since


cannot


considered


as an "electron


Comparison o

for a particular


f data


for gas-phase


redox couple


leads


and solution-phase entropy

to the separation of the ob


changes

served


entropy


change


in solution


into an


intramolecular


contribution,


plus


contribution


from


solvent


polarization.


Such


comparisons


can not


only


provide

electron


considerable


attachment


insight


to gas-phase


into the magnitudes of


coordination


entropy


complexes,


changes


also


lead


to a greater understanding


of the role of


the solvent


in determining the


overall


change


in entropy


for a particular


redox


couple.


Presented here


are the results


statistical mechanics


calculations


of the entropy


changes


involved


for electron attachment


some gas-


phase octahedral


complexes.


The examples


given


are for complexes


that


form stable


redox


couples


in solution.
__ t- i2-


Calculations


are


repeated


- J f


and Fe(CN) 4/3"


B












performed


WCI 6

data


for the


aions


. Comparisons


obtained


here


in the couples


are made,


where


and the experimental


Ru (NH3) 63+/2+


possible,


data


, CO(NH) 3+/2+


between


reported


the theoretical


in the


literature.


insight


gained


used


to provide estimates


for the


gas-phase


entropy

M(hfac)3


changes


that


occur


for electron


attachment


to M(


acac)3


complexes.


Statistical


Gas-Phase


Redox Couples


Mechanics Applied to


Intramolecular


the Determination


Entropy Chanoes


Involving Complex Metal


Ions.


Electron attachment


to coordinated


transition metal


centers


is often


into


a metal


based molecular


orbital.


changes


in metal-ligand


bonding that

vibrations,


result

change


can shift

the moment


the frequencies

of inertia of


of metal-ligand


the molecule


skeletal

shifting


metal-ligand bond


lengths


and change ground


state


electronic


degeneracies.


These


internal


rearrangements


redistribute


internal


energy
change

solvent


of the molecule or


(gas)0).


ion and lead


total


can be expressed as


vibrational


electronic


change


an intramolecular


in entropy


sum of


entropy


in the


translational,


contributions


entropy


absence of


rotational,


(eq 4-1)


AS,(gas)0


= As


trans)0


+ ASi(rot)0


+ AS1(vib)0


+ AS (elec)0


contributions


AS1 (trans)0


, ASi (vib)0


, etc.


for ideal


gases


can be


evaluated by

Thermodynamic


using


the methods


functions


can be


of statistical


readily


thermodynamics.


calculated


from


appropriate


partition


function


Svib'


etc.)


which


a summation over


available energy


states


that


are thermally populated,


4-2.


( qt rans'












value of


q in eq


4-2 at


a given


temperature


is dependent


on the


degeneracy


of the energy


states,


and the energy


separations


between


states,


The term k


is the Boltzmann


constant.


The general


express


sion for the


rotational,


vibrational


electronic entropies


a system of


ideal


gaseous


particles


given


4-3.


(E-E0)


+ R lnq 4-3


values


of AS4(rot)0


, AS4(vib)0


and AS


elec)


for gas-phase


electron


attachment


Si(rot)


to a molecule can be


, S(vib)


and S


-(elec)


found


for both


from eq


4-3 by


the oxidized


calculating

and reduced


species and


obtaining the difference between


the values


for each


species

the two


STo evaluate the


terms on


is the thermal


energy


various


right of

and may


contributions


eq 4-3


also be


must


to ASi (gas)0


be evaluated.


separated


into


, therefore,


The term


(E-E0)


(E-E0) trans'


(E-EO)rot,
partition


etc.


Thermal


energies


function given by eq


are calculated


from the


appropriate


4-4.


(E-E0) -RT2 dln
a dT


In statistical


thermodynamics


calculations of


entropies,


expressions

treating the

oscillators.

accuracy of


used


for AS (rot)0


complex as


a rigid


and ASi(vib)0


rotor


Corrections can be made,

the calculations is small


are


approximations


and the normal modes


but the


improvements


are not included


based


as harmonic


in the

in the


discussion


here.


The contributions


from ASi(trans)0


rot)0













Chances


In Translational


Entropyv


The tr

particular

particles.


anslational


entropy


temperature and


a system of


volume


Electron attachment


related


to a molecule


ideal


particles


to the mass


of the


has a negligible


effect


the mass


the resulting


change


in AS


(trans)0


is also negligible.


evaluate


gas)0


, therefore,


no consideration need be given


AS. (trans)0


However,


values


of gas-phase entropies


of single


ions


given


this


below


purpose.


for completeness


The values


and a


reported


value of


(trans)0


in the present


required


work are


given by the


Sackur-Tetrode equation given


Stan
trans


4-5.


/3
5( 2i-mkT T
--2
2 \lh2


m is the mass


of the particle


k is the


Boltzmann


constant,


is Plank's


constant


, V i


volume of


the gas


and N


Avagadro's


constant.


Chances


in Rotational


Entropy


The expression


is obtained by


substituting


the quantum


mechanical


expression


for rotational


energy


spacings


into eq


4-2.


Since


rotational


energy


space


ings


are very


small


compared


to kT,


summation


can be


replaced by


an integral.


The result


is given


4-6.


- 82 (IBC) 3/2(2xkT)3/2
oh2


Octahedral


molecules


are classed


as spherical


tops


three


principle moments of


inertia


are the


same.


term


4-6 is


are


r(





L












octahedral molecule.


Substitution


eq 4-6 into eq


4-4 yields


following expressions


for the rotational


thermal


energy


((E-Eo)rot)


mole


degree of


freedom.


[E-E0 rot


= RT/2


For all but


the lightest


ions


and molecules


the moment


of inertia


large

value


enough

of RT/2


that


the rotational


per degree of


thermal


freedom.


energy


attains


For molecules


with


its classical


a low moment


inertia


integral


summation


and must


4-2 cannot


be evaluated


be accurately


either manually,


replaced by


or by using the Euler


Maculaurin


summation


formula.


For this


case the


thermal


energy of


is slightly


less


than


the value


4-7.


For molecules


rotational


3RT/2


applies


such as


freedom


to both


octahedral


the thermal


energy


the oxidized


complexes

is 3RT/2


and reduced


that


have


Since

complex,


degrees

value of


only


ARln


4-3 contributes


to ASi


rot)0


Substituting


eq 4-6 into eq


4-3 gives


an express


ion for AS


roto


for electron attachment


to octahedral


molecules


, eq


- 1i (Inc( (ed)-I c(ox)


( 8xkT
\ 2 )


terms


IABC (red)


and IABC


3(ox)


are the moments


of inertia


for the


reduced


and oxidized metal


complex


respectively.


In Figure


4-1 a plot


is shown


of the


rotational


entropy


, given by eq


4-3,


for the molecules MF6,


MC16


and MBr6


as a function


of increasing


distance


at 298 K.


It can be


seen


that


all the


plots


are


AStor












the plots


is close to


at 2


A and


varies


little over the


range


shown.


This


sets


an approximate upper


limit


of AS-(rot)0


- 0.6


cal mol


for octahedral metal


complexes


precise


value


can be calculated


from eq


4-8.


For the complexes


considered


in thi


chapter the M-L


bond


lengths


required


literature


data


for the evaluation


sources


are from X-ray


of rotational


and the data are given


crystallography


studies


entropies

in Table


except


were


4-1.


W-Cl


obtained


bond


bond


from


length

length


in WC16,


which


was obtained


in the ga


s-phase by


an electron


diffraction


study.


Values


are not available


for the M-L distances


in IrCl6


WC16


values


given


for the


ions


in Table 4-1


are estimated


values,


obtained by


adding 0.05


to the


values


for IrCl6


WCl5


respectively.


For both


ions the


electron


in the


lower


oxidation


state


complex


accommodated


in the


t2g non-bonding


orbital


set.


Where


structural


data


are available,


this


change


in M-L bond


length


is typical


ions


that


are stable


in oxidation


states


of similar


electronic


configuration.

these estimates


The error


is small.


introduced


in the


value


For the hexacyanoferrate


for AS (rot)0


from


complexes


rotational


entropy was


calculated


considering


each


cyano


group as


having


an atomic mass


of 26.02


amu and


situated


at the


average distance


of the C


and N


atoms


from the metal


center


(see


Table


4-1)


ammine


complexes,


rotational


entropies were


calculated


from an


effective M-L


bond

mass


distance obtained


amu.


by treating the


ammine group as


The effective M-L distance was


calculated


a single


atom of


from


appropriate M-N


and N-H bond


lengths


given


in Table


4-1.


for MX6












Table


4-1.


Metal-Lipand


Bond LenQths


in Metal


Complexes.


Complex

IrC162-

IrC1 3-
WCl6


WCl6

Co(N16 )

Co(NH3);


Bond Length/A


(M-L)


(M-L)


.307a8


.357 0


(M-L)


(M-L)


(M-N)
(N-H)
(M-L)


.114e
.010g
.173h


Co(NH3


(M-L)
(N-H)
(M-L)


8Values


taken


.936'
.010g
.995h


from ref.


Complex

Fe(CN)6


(M-C)
(C-N)


Fe(CN)6


(M-C)
(C-N)


Ru(NH3)6


(M-N)
(N-H)
(M-L)


Bond Length/A


.936a
.191a



.9008
.138a


.144f
.010g
.203h


NH3)6


(M-N)
(N-H)
(M-L)


.104f
.010*
.163h


Value
CValue

value

value


estimated by

in gas-phase

estimated by


fValue of

Value of

hEffective


distance

distance

distance


value


adding 0

from ref


adding


.05 A


value for IrCl6


(see


text)


107.


.05 A


to value


for WCl6


from

from

from


center


mass


calculated


from M-N


and N-H


distances.


.26c


.31d
















29-

28-

27

26-

'i
o 245
'*24
- 23-
0
22,

21

20,
1.8


Slope


2.98


1.9 2.0 2.1 2.2 2.3 2.4 2.5


- MBr6



-MCI6






2.MF6


2.6


M-L


Distance/A













Resulting values


Table


, with


of rotational


values


entropies

the total


for the


standard


complexes

gas-phase


are given

entropies,


ASi(gas)0


Chances


in Vibrational


Entropyov


expression


given


in eq


1
m
1-e -x


Vibrational


summation


given


energy


in eq


spacings


4-2 can not be


from a binomial


are typically


replaced by


expansion


larger than


an integral.


In eq


kT and


Equation


term x


4-9 the


hcu/kT,


in which


U is


the frequency


of the


vibrational mode


C iS


speed

can be


of light.

found by


vibrational


substituting


thermal


energy per


into eq


4-3.


degree of


result


freedom


is given


4-10.


[E-Eo


vib


x RT
ex-1
x*"


4-10


Since


the magnitude of


vibrational


energy


spacings


are typically


close


or larger than


value of


(E-EO)vib


some


fraction of


RT per


mol,


occur


per degree of

on electron


freedom.


attachment


Changes


cause


in vibrational


a change


frequencies


that


in both


and both


terms on


the right


4-3 therefore


contribute


to ASi(vib)0


Substituting


the expressions


for (E-E0)vib


into


-4 gives


expression


for As.(vib)0


4-11


w r,[


xR Xo


,_ 1


1


If


|1


E-E)Ovib


n n


R


















5.5

5.0
4.5

4.0

3.5
I

2.0
- 2.5
o

o
01.5

1.0

0.5
0.0


0 200 400 600 800 1000ob


1200


Vibrational freq./cm












oxidized and


reduced


species,


the frequencies


of which are


included


The definitions


and x0


are the


same


as that


given


but apply to the


reduced and


oxidized


species


respectively


The vibrational


characteristics


of metal


complexes


suggests


that


vibrational


entropy


changes


can be


significant


in certain


cases.


Figure


4-2 vibrational


entropy


is plotted as


a function


of vibrational


frequency


at 298 K.


It can be


seen


that


S,(vib)


increases


dramatically


as the


frequency


a vibrational mode decreases.


For


organometallic


coordination


compounds,


vibrations


associated


with metal-ligand


skeletal modes


are typically


in the


range of


100-700


-1. Shifts


these


frequencies,


oxidation


state at


of the magnitude


the metal


center,


that


can


occur


cause


for a change

significant


in formal


changes


entropy


vibrational mode,


especially


at low frequencies.


Moreover,


a non-linear molecule has


3N-6


vibrational


modes


(where N


is the


number


of atoms


in the molecule)


For MX


octahedral


complexes


there


therefore


a total


of 15 skeletal


vibrations


that


enter


into


summation


4-11.


Vibrational


frequencies used


to calculate the


vibrational


entropies


for the


complexes


considered


in thi


chapter


are given


in Tables


4-2 to


4-4.


assumption


is used


throughout


that


vibrational


frequencies


reported,


observed


in solution and


in the solid


state,


are


same


their


gas-phase values.


Since


a small


dependency


on the polari


zing


nature of


counter


ions


observed


for solid


state


spectra,


solution-


phase data


are used


wherever possible.


The only


frequencies


used


that


are obtained


from solid


state


spectra


are for the


IR active Tu modes.


These


possible


are the only


skeletal modes


IR active vibrations


for MX6


complexes


and account


for 6


12 of the


33 possible


S 0 0 0


are


* -


1












Table


4-2.


Assignments


Hexachloride Metal


of~~ ~ ~ Virrn( rrin aIi1'


Complexes


IrCl6'

IrCl6


a 353


WC16a 437


WCl6


aFrequencies


taken


from ref


111.


bThe T2 bend
16 "J6-12),


a infrared
see text.


and Raman


inactive;


value obtained


from


CFrequencies


taken


from ref.


112.


dValue


from


ref.


113.


129b


c^m~1\


of Vibrational


Fre uencies


139b


168d












Table
Metal


4-3.


Assignments


of Vibrational


Frequencies


(cm~1)


for Hexacvano


Complexes


Fe(CN


Skeletal M-C
Vibrations


M-C-N
Vibrations


C-N
Vibrations


2136


2136


2105


Fe(CN)6


Skeletal M-C
Vibrations


M-C-N
Vibrations


C-N
Vibrations


2080


2048


2033


351b


381b


350b


402b












Table 4-4.


Metal


ComIol


Assignments


of Vibrational


Frequencies


fcmn 1)


in Hexammine


exes


NH3) 6


Skeletal M-N
Vibrations


Ammonia


Rocking
Vibrations


788c


788c


Ru(NH3)6


Skeletal M-N
Vibrations


Ammonia


Rocking


769c


769c


769c


170e
270e


170e
270e


175b


788c


409d


120b
190b












Table 4-4


continued.


Co ( NH3 ) 63' a


Skeletal


Vibrations


Ammonia


Rocking
Vibrations






Co(NH3)62+,a

Skeletal M-N
Vibrations


830c


830c


187f


Ammonia


Rocking
Vibrations


654c


654c


654c


aFrequencies


taken


from ref


balue


for 06 obtained


from


6 = U5(2"1/2)


see text.


CT and T
value may
as the T


rocking vibrations
* unavailable. Fre


mode given


in ref.


are infrared


quencies


given


and Raman


inactive


are assumed


to be the


Tsme
dime


116.


Only


available


frequency


, from


, others


estimated.


228b


132b


__


k












limit


placed


on all estimated


frequencies


is 10%.


The most


potentially


serious


error


in the calculation of


vibrational


entropies


comes


from the estimated


frequency


of the inactive


skeletal


bending


mode.


The frequency


of this mode


is typically


in the


region


or so and any uncertainty produces


a large error


in the


vibrational


entropy


(see


Figure


4-2)


For most


the complexes


in Tables


4-2 to 4-


the skeletal


Tu mode was


obtained


from the


relationship


relationship


correctly predict


predicted


values


theoretically


some XY6


and has been


compounds


shown


in which


central


atom has


a closed


shell


electronic


configuration.


octahedral


transition metal


hexafluorides,


for which


is available


from combination bands


relationship


is generally


or resonance


observed


phosphorescence


to hold


to within


spectra, t

the error


limits


10% given


here.


Ru(NH3)6


data


not been reported,


for the


except


frequencies of


for the Tu mode


(see


skeletal modes


Table


have


4-4)


frequencies


given


Table


4-4 are estimations


based


on calculations


observed


frequencies


for other


hexaammine complexes of


ions.


addition


to the skeletal modes


given


for the


hexaammine


complexes


Table


4-4,


frequencies


are reported


for the


ammine


ligand N-H


rocking


vibrations.


Unlike


skeletal


modes,


these


frequencies


are


available


for Ru(NH3)62.+ 116


The N-H rocking vibrations


are


the only


other


vibrations


of low enough


frequency to contribute


significantly to


vibrational


entropy


for these complexes.


There


are a total


of 12 modes


and T2 )


of which only the


and T2g modes


are


infrared


Raman


inactive.


These


frequencies


are observed at


830cm


respectively


for Co(NH3)63


but only the


infrared


active


Tu modes


1/2)


are


= u5(


(Tlg,












Chances


in Electronic


EntroDv


Electronic energy


separations


are usually


large


compared


to kT


exponential


term


4-2 is therefore close


zero


usually


equal


to the degeneracy


the ground


electronic


state


maximum possible degeneracy


an electronic


state


is given by


product


of the


total


spin


and orbital


degeneracies.


required


information


carried


in the


spectroscopic term


symbol


for the


state.


Under the octahedral


symbol


point


group the orbital


singly degenerate


, doubly


degeneracy

degenerate;


denoted by


, triply


degenerate.


total


spin


degeneracy


(multiplicity


given by


2S+1


where


S is the


total


spin


angular momentum and


is denoted


in the


superscript


preceding the orbital


symbol.


spectroscopic


term


symbols


the metal


for octahedral


d orbitals


complexes


in an


are derived


octahedral


ligand


purely

field.


from


symmetry of


In reality


, the


degeneracy of


the electronic


ground


state


a particular


complex


can be


split

of the


n energy

complex


The extent


the nature of


the splitting


the electronic


depends


state


on the


structure


itself.


ground


state


electronic


degeneracy


of the complex may therefore


be less


than


value


suggested by the


spectroscopic


term symbol,


since


it is


dependent


on the thermal


population


the energetically


split


states.


There


are two


principle effects


that


contribute


to the


splitting


orbital


degeneracies,


spin-orbit


coupling


and distortions


from perfect


octahedral


symmetry.


Spin-orbit


couplin.


coupling of


spin


and orbital


angular


moment


of the d


electrons


results


a splitting of


electronic


degeneracy


For A and E ground


states


there


no orbital


angular


momentum


consequently


no spin


-orbit


coupling


For T ground


states


qetec












state,


value of


the Racah


electronic


repulsion


parameter


the magnitude of


ligand


field


(10Dq)


For second


third


metals


the effect


is greater


and orbital


splitting


are generally


in the


range


of 500 5000


Distortions


from octahedral


symmetry.


Molecules


that


have orbitally


degenerate ground


states


have


a tendency to


physically


distort


to move


to a


state of


lower


energy


and lower


symmetry,


removing the


orbital


degeneracy

Jahn-Teller


of the state.


theorem.


119,120


This


statement


The effect


a simplified


is observed


form of


to occur


octahedral metal


ground state


complexes

not purely


For example,


octahedral


Ti(H20) 6


and the


which


has a 2Tg


orbitals


are


split


into a


set of bl,


states.


single electron


resides


in the lowest


energy


orbital.


Similarly,


for ions


such


, a pure octahedral


ligand


field


would


produce


a degenerate


of orbitals


containing three electrons.


From experiment,


the orbitals


found


to be split


such


that


the unpaired


electron


resides


a state


single


orbital


degeneracy.


The magnitude of


the orbital


splitting


typically


in the


range of


about


several


hundred


wave


numbers


up to


about


2000


(observed


for Cu2+


complexes)


so are comparable


to the


magnitudes

complexes


of splitting


symmetry)


due to spin-orbit


a trigonal


distortion


coupling.


is possible


tris-chelate


if the


"bite


angle"


of the ligand


not precisely


In this


case,


the degenerate


set (octahedral


symmetry


is split


into a


set of


orbitals.


set in octahedral


symmetry.


M(acac)3


An example of


complexes


has been


symmetry remains


the degree of


reported


a doubly

trigonal

Co(acac)3


degenerate

splitting


E set in


crystal


structure of


Co(acac)3


reveals


an average O-Co-O bite


angle


of 97.3


A'


. S 1 -.


row


are


+ eg


q


4R












The geometry


of the complex


in the gas-phase


has not been


reported.


The entropy


an electronic


state can


be evaluated


from


4-3.


the absence of


a thermally


acce


ssible


higher


lying


states,


entropy


of a ground

degeneracy


states


of the


electronic s

of the ground


is possible,


thermal


tate


is given by


state.


the entropy


population


If thermal


of the


of the split


= R In


population


state must


states;


where g


of higher


be considered


that


the

lying

in terms


electronic


partition


function


(qetec)


must


be evaluated.


An orbitally


split


state


that


can be


thermally populated


will


also


posess


a thermal


energy


((E-Eo) etec)


This


thermal


energy must


also be


considered when


evaluating the entropy


of the state


, as defined by equation


4-3.


example of


the relationship between


the entropy


an electronic


state


and the


splitting of


temperatures


AE = 0


is given


entropy


the degeneracy


in Figure

given by


of the


state


4-3 for the example of


= R In


and for a 2E


an energy


a 2E


state


at two


state


this


equal

shown


to R In 4


75 cal


in Figure


mol"


As AE


splitting of


increases


value


state


gelec'


given by


approaches


+ e-ERT),

a value of


rapidly decreases


R In


(1.38


and R


cal mol


rapidly


as shown


in Figure 4-3


AE > 0


approaches

thermally


(E-Eo) etec


as AE becomes


accessible.


increases


so large

value of


, reaches


that


(E-EO)elec


a maximum


upper


value,


state


and then


no longer


is given by


+ e(AERT))]


AE and has been


shown by


Lias


and Ausloos92c


reach


a maximum of


-0.2


kcal


mol-1


for a 2E


state.


contribution


the entropy


is given


from


(E-E0)etec/T,


which


is also


shown


in Figure


overall


effect


on the entropy


of the


state


is that


it also


converges


on the value of


R In


, but retains


a significant


amount


= 2(


qelec


qe te


[(e(-AE/RT)) /










































350
298


U-


R Inq


(R





(E-Eo)/'T


- -
a- -t


- a-
C--


0 200


a


e-...


=












splitting.

states is


At absolute


possible


zero


no thermal


and the entropy


of the


population


state


of higher


given


lying

the


degeneracy of


lowest


lying


state.


Assess


inar the entropies


of electronic .round


states.


combined


effects


give


of spin-orbit


a characteristic


coupling

splitting


and distortions


of electronic


from octahedral


symmetry


degeneracy


particular metal


complex that


dependent


on the metal


ion,


oxidation


state


and the nature of


coordinated


ligand.


Since


energy


spacings


are typically


on the order


of magnitude


of kT,


a range


of states


in the electronic manifold


can be thermally populated,


depending


on the


resulting


energy


spacings


and the temperature.


increasing population

particularly manifest


susceptibility


of higher


lying


states


with


temperature


in the temperature dependence of


transition metal


the magnetic


complexes.


In Table


4-5,


estimates


are given


for the


change


in electronic


entropy


for the redox


couples


containing the


octahedral


ions


cons


idered


here.


For the


complexes with A and E


ground


states,


the orbital


angular


momentum


spin-orbit

electronic


function


orbital


is quenched


coupling.

state was


equal


and so the electronic


For A ground

estimated by


to the spin


degeneracy may


be split


states,


degeneracy

therefore,


assuming that


degeneracy.


by distortions


is not split

the entropy


the electronic


For E ground


partition


states,


from octahedral


symmetry.


The entropy of


state depends on


the thermal


population


of the


upper


state.


separation


As shown


in Figure


between


4-3,


states


for typical


, the


upper


values


state


of the


can be


energy


accessible


ordinary


temperatures.


Since the


energy


spacings


between


split


states


are not known,


the entropy of


E states was


estimated


from












Table 4-5


Electronic


Entropy Chanqes


For Redox Couples.


Change in
Electronic


Redox


Couple


Ground


State


soln)


(elec)'

.78 1


IrCl6

WCl60


(soln)


(soln


-1.78 1


1 -0.58 2


Co (NH3 ) 63+/2+

Ru (NH3) 63+/2+


(soln)

(soln)


1 2

1 -1


.48 2


.78 1


Sc(acac)


acac


V(acac)


Cr(acac)
Mn(acac)

Fe(acac)


acac)


(gas)
"(gas)

(gas)


.78 1

.41 3

.58 2

.15 0

.34 0


0/-(gas)


(gas


(gas)


.87 + 2

.48 2


(gas)


8Values


are


convention.


in cal mol"1


Entropy of


Calculated


the free


electron


ox + e


- red


is not included


in the


'e(CN)63-/4-


-, 3T

- 4T


2T2
-* 3TI

4 A2
- 5E

-, 6A1


- 4T1












states


split


spin-orbit


coupling


can have


a lower


degeneracy than


spin


degeneracy122


and a realistic evaluation


of the


range of


values


the electronic partition


function


is difficult


to estimate.


For the


complexes


that


have


ground


states


in Table


4-5,


the electronic


entropy


estimated


from a


value


the partition


function


taken


as the


average of

appropriate


to the maximum degeneracy of


term symbol.


Estimates of


state,


electronic


as given by the


energy


spacings,


hence


the electronic


partition


function,


can be obtained


from matching


the observed


complex


temperature dependence of


to the theoretical


temperature


the magnetic

dependence,


susceptibility


derived


from


theoretical


energy


spacings,


but such


data


are scarce.


Comparison


of Solution-Phase


Redox


Couples


and Gas-Phase Entropy


Involving Octahedral


Metal


Changes
Complexes


for Some


Entropy Chanaes


for Solution-Phase Redox Couples


The experimental method


for obtaining


entropy


changes


for half-cell


redox


couples


involves


the use


of cyclic


voltammetry


in a non-thermal


cell


arrangement


that


permits


temperature of


half-cell


containing


the redox couple of


interest


to be varied,


while the


temperature of


the other


half-cell,


containing the


reference


electrode


is held


constant.


The method


provides


a simple means


to evaluate


difference between


the absolute


ionic


entropies


of the


reduced and


oxidized


halves


of the couple


given


AS,


0
- Srad -


4-12


Interpretation


of entropy


changes


for redox


couples


involving


was












complex


ion.


However,


dielectric


continuum models


have not


provided


adequate description


of observed


o values.


In particular,


anomalous


entropy


changes


assoc


iated with


Co(III)/Co(II)


couples


comparison t

quantitative


for redox

mechanics,

estimated.


o analogous

explanation


couples


Ru(III)/Ru(II)


involving


intramolecula


y calculating

coordination

r and solvent


couples)


have evaded


intramolecular


complexes


satisfactory


entropy


by using


contributions


changes


state istical


to ASrc


can be


Several


values


have


been


determined by


various


workers


selection of


results


for various


redox


couples


are given


in Table


4-6.


solvent


for all redox


couples


in Table


4-6 is


water.


Also


given


in Table


4-6 are the


theoretical


values of


0 predicted by the


Born


equation


(ASBorn0).


Born equation124


is based


on a purely


electrostatic model


can be used


to obtain


the change


in free energy


entropy when a


charge


is transferred


from a


conducting


sphere


vacuum to


an identical


sphere


in a medium of


dielectric


constant


e (eqs


4-13


4-14).


AGnorn


- -_ 21--
2r\ e


4-13


AS Brn


- -P
^ BoX 1
" t aT ) p


- q2 1ne
2iTe 81nT J p


4-14


In eqs


4-13


4-14,


the charge on


the conducting


sphere


e iS


the dielectric


constant


of the medium.


When


the medium


water


at 25C


written


spheres

in the


are


ions


convenient


of absolute


forms of


charge


4-15


ze, eqs


4-13


4-14


can be


4-16.












Table


4-6.


Experimental


and Theoretical


Entropies


Redox Couples.


Redox Couple


ASBorn


0
ASBorn0)


A (M-La .)
D iasance


Ru (NH3) 63+/2+' C

Os(NH3)63+/2+


Co (NH3) 63+/2+


Ru(en)33

Co(en)33

Ru(H20)6


18.5


18 0


d 45


+/2+


13 0


37 2


3+/2+,c


38 3


14.6


14.6


14.6


13.0


13.0

14.6


14.6


CO(H20)3+/2+,d
Fe(H20)33+12+,b


bipy) 33+12+


14.6


28.4


c 1


-0.048f


Fe(bipy)33+12+,c

Co(bipy)33+/2+, c

Fe ( CN) 63" 14 -, c


22


-41.5


aAll


values


given


in cal mol


bata

CData


from ref

from ref


dFrom ref


eData

Data


103.

104.


. 105 (value estimated by


from Tabi


from ref.


authors)


4-1.


123.


.040e


0.178e


+/2+,b


-0.036e













ASforn


z2
- -9.649 -z-
r7A


cal mol-1


4-16


Born


equation


is most


successfully


applied


to large


approximately

solute/solvent


spherical


ions


interactions


of low charge,


are absent.


and where


For these


specific


ions,


the effect


changes


in size of


the ion with


changes


in the oxidation


state of


metal


the effect


of dielectric


saturation


are both minimized.


should be


noted


that


for the


reduction of


a complex


bearing


a positive


charge

bearing


sign


of ASBorn


a negative charge,


positive.


sign


For neutral


of ASBorn


complexes


is negative.


those


A more


positive entropy


can be associated


with


ions


of lower


charge,


since


there will


be less


"ordering"


of the surrounding


solvent


molecules.


Comparing the experimental


and theoretical


entropy


changes


for the


redox


couples


in Table


4-6,


it is


seen


that


there


is generally


a poor


agreement


between the


two values.


However,


the theoretical


value


serves


as a reference


point


to which


the experimental


values


can be


compared


absence of


specific


solute-solvent


interactions.


sign


magnitude of

information


the deviations


about


the nature and


of experimental


the extent


results


of the


from ASBorn


changes


o provide


in specific


solute-solvent


interactions


that


occur


on reduction


a particular


metal


complex.


The difference between


ASBorn


for each


couple


is included


in Table 4-6


for this


purpose.


It is particularly


interesting to


note


in Table


4-6 that


for the


couples


Ru (bipy) 3+/2+


(where bipy


'-bipyridine)


which


bonding,


the nature of


that


the M-L bonding


value of


is more


- ASBorn


complex


than


is negative.


simple


For each


of these


Fe(CN) 3-4-












energy match


with


ligand


r orbitals,


and subsequently


an overall


increase


in the degree of


and Weaver


to account


(M-L)


for the


bonding.


negative


A related


value


argument


of ASrc


was


used by


- ASBorn


the Ru(bipy)332

are in operation.


couple.


was suggested


The water molecules


close


that


to the


competing


effects


ruthenium center,


including

therefore


those

less


surrounding the


"ordered"


ligands,


in the lower


will


oxidation


be less

n state,


polarize

giving


rise to


positive


contribution


to ASr


However


, the water molecules


adjacent


to the bipyridine rings may experience


an increase


in polar


ization


going to


the Ru(II)


state


since


the added


electron


will


significantly delocalized


around


aromatic


rings,


acting to


increase


their


net charge den


sity.


The latter


contribution


would


give


a negative


contribution


to ASrc


An opposite


effect


was


used


'to describe


anomalously


large value of


for Co (bipy) 33+/2+


Co(III)


Co(II)


reactions


involve


the electronic


convers


ion t2g


- t29g


which


should minimize


the extent


of electron


delocaliz


action


in the


reduced


state


and therefore discourage


crease


solvent


polarization


the vicinity of


the bipyridine


rings.


Further,


the expansion


at the


metal


center was


suggested


to lead


an especially


large decrease


polarization


for the


negative


of nearby water molecules.


value of


- ASsBorn


It seems that


o for the Ru(bipy)33+/2+


e arguments

couple are


not without merit,


conceive.


since


The explanation


an alternative explanation


for the Co(bipy)33+/2


is difficult


couple may


questionable,


cal mol"1


however,


between


since


the large difference of


the Ru (bipy)33'+/2


and Co (bipy) 33+12+


approximately


couples


consistently


found


for other


couples


involving


reductions


at Ru(III)


CO(III)


centers where only


M-L


o bonding


is possible.


seems


that












Intramolecular


Contributions


to ASrc
rc-


Single


ion hydration


entropies


have


been


obtained


for many monatomic


polyatomic


ions


by evaluating the


entropy


change


for the


transference


a gas-phase


ion M of


charge


n to the


solution


phase


according to

the reaction


the reaction Mn(gas


- Mn(aq


) 125-128


value of


given by


AS (hyd


i (gas)


i(aq


4-17


o+ 6.35 cal mol-1 K-1


value of


6.35


cal mol-1 K-1


(R In 24.41)


arises


from the different


standard

Si(gas)0


states


and Si(aq)


for the gas-phase


for a particular


and the


solution


phase.


ion are typically


value of


quite


different,


value of


S1(aq) being


smaller


and often


negative.


Translational


freedom


is restricted


and it is uncertain how


rotational motion will


affected.


Also


the difference


polarization

in entropy of


of the solvent may


an ion between


contribute greatly to


phases.


Although


aq)


data


are available


for a large number


polyatomic


ions,


there


are apparently no


aq)


for ionic


reports

species


on comparisons made between ASi(gas)0


in redox


couples.


results


of the


calculations that


yield


gas-phase


entropies of


the octahedral


complexes


considered


in the


present


work are


presented


in Table


From


the results


of the calculations


it can be


seen


that


trans)0


same


within


for the oxidized


cal mol


and reduced


(Figure


4-1)


species,


that


Si (rot)0


can be anticipated


that


these


terms


will


also


remain


constant


between


the oxidized


and reduced


species


in solution.


Much


larger


differences


in entropy


can potentially


arise from S


vib)


and Si


elec)0


, and the


calculated


gas-phase


values














AS


- ASi(vib)


o + ASi(elec


0+ ASoolv


4-18


4-18,


ions


in the


ASsolv

redox


is the difference


couple.


There


in the entropy


are two situations


solvation


of the


where the


contribution


o to


can be


separated


from ASrc


so that


contributions


of large


radii


from AS.

, ASsoLv


vib)


and AS.(elec)0 may be estimated.


in water


predicted by the


Born


equation


ions


(4-16)


to be small


comparing


and therefore


two redox


couples of


= AS1(vib

different


+ AS4(elec)


metal


ions


Also,


when


coordinated by the


same


ligand,


and undergoing the


same


change


in oxidation


states,


Assolv


is constant


and AASrc


= AAS.(vib)0


+ AAS.(elec)0


It is illuminating to


calculations,


obtained


which


aqueous


compare the


are given

solution,


in Table


which


results of


4-7,


are given


gas-phase


to the experimental


in Table


4-6.


results


For the


ions that


form


the redox


couples


Ru (NH3) 63+12+


, IrC12"


, WCl6


the difference


in gas-phase entropies


is small


therefore


only


Ssolv0 will


ASi(gas)0

value of


= 17.8


gas)0


contribute

cal mol"1 E


can be


to ASrc.


For the Co(NH ) 3+/2+


The origin


traced


of the


to the difference


couple


comparatively


in spin


large


states


between


bonding

result


the oxidized


and reduced


significantly weakened


of the doubly


occupied


species.

relative


In Co(II)

to Co(III)


antibonding e metal


comply


exes


complexes


based


orbitals


the M-L


as a


in the


Co(II)


state.


As a result,


the skeletal


vibrational


modes


are shifted


to substantially


lower


frequencies


and a large


increase


in vibrational


entropy re

also gives


sults.


rise


The greater

a significa


electronic

nt increase


degeneracy


ASi(elec)0


of the Co(II)


(Table


state


4-6).


1wL I -. *


t I e~.


S U


Fe(CN) 3"/4"























































C o
M -
1 0

w in
-4 9.-
o
rS Ca


to o
* .
0,4
OH-M

40 (^ r-4


,-* I
e1
0I I
CE


r-i |
I I
rEO u


+ +1"


(Ned


n9 (n -











(1,10-phen)

frequencies

observed at


complexes


of the


For Fe(bipy


384 and 367 cm-1


same metal


infrared


ion have


active M-N


For Fe(bipy)32+


similar M-L


vibrations


these


vibrational


are


frequencies


are


shifted


slightly to


386 and 376


respectively.


Co(1,10-phen)3


similar


frequencies


to these


are observed at


378 and


cm-1,130 but

frequencies


for Co(bipy)3


are shifted to


at 266 and 228 cm"1


Large


substantially

contributions


lower

to vibrational


entropy


can be generally


expected


for cobalt


couples


that


undergo


same change

vibrational


reduced


in spin


stat


frequencies


species


are


e, although a


that


required


complete


are different


set of data


between


to quantitatively


for all the


the oxidized


evaluate As


(vib)


all the


same


redox


spin


couples

change


involving Co(III)/Co(II)


involved


and values


reductions


for As rc


are


in Table


constantly


25 cal mol


higher than


corresponding Ru(III)/Ru(II)


couples.


The difference

and Ru(NH3)+2


15.4


in the values of


obtained


cal mol1


intramolecular


ASi (gas)0


for the


from the calculations


result


entropy


changes


demonstrates


for Co(III)/Co(II)


couples


Co(NH3)63/2


in the present

importance of


redox


work


couples,


offers


a feasible explanation


and Co(III)/(II


of the large differences


redox


couples


studied


in ASrc

aqueous


for the


solution.


Relationship


Between


Free Enercv


and Enthalov of


Gas-Phase Electron Attachment


to M(acac)3


and M(hfac)3


Complexes


The electron


attachment


energies


quoted


for the M(acac)3


M(hfac)3
at 350 K.


complexes


The data


in the present


would


serve a


work are


wider


free energies


range of


(AG )


obtained


applications


I- harmnr~hom nr Ae0 RnA AR0 nan I A ha nhl- ni nail n* al-bar


if vanluia nf


Ru(III)/(II)


A o n/I AW 0












data.


Values


for AH


at 298.15


K can be


readily


combined


energy


cycles


with


compiled


data


for other


processes.


The relationship between


an experimental


temperature


(Texp)


and AHl
a


and AG0


different


temperature


is given


in equations


4-19


4-20


AG (T


- AG(T


+ AS0 [Texp


T
- Cp(M)dT+
T


T1
fCp(M-) dT
T


4-19


AH (T)


- AG(Te,


+TexpAS


T
f Cp (M) dT
T


T
fCp(M-) dT
T


4-20


It is often assumed


that


temperature dependence


and AS


electron


attachment


or ionization


a neutral molecule


is negligible


For example,


for electron


= the electron


used by


capture

affinity


Kebarle to quote electron


a species


affinities


M to


form M ;


equation

E organic


4-20


AGe(0


been


compounds,


neglecting


the integral


terms.


Lias


and Ausloos92c


have explored


validity


of this


assumption by performing


statistical


thermodynamics


calculations


on several


organic


and inorganic


compounds


from


spectroscopic data.


As shown


above,


and stated more explic


itly


Lias


and Ausloos, t

energy between


he difference

a species M a


in translational

nd its ion (M o:


and rotational


r M')


thermal


is negligible.


Differences


can only


arise


from


(E-Eo)vib


(E-EO)etec


Under the


convention


volume of


the electron


zero


so for electron


attachment


AP =AV


= 0.


Therefore,


- Cp


and AE


= AH.


Lias


Ausloos


showed


difference


that


between


from the compounds


adiabatic


they


ionization


studied,

potential


largest


enthalpy


of ionization of


enthalpy


at 350


arose


for ethylene,


which


a a- o 1 -












4-20


can be


expected


to be significantly


greater than


absolute


magnitude of


sum of


the integral


terms.


From


calculations given


above


for pairs of


octahedral


transition metal


complex


ions


that


form


redox


couples


(Table


4-7)


can be


seen


that


where


acceptor


orbital


is a non-bonding metal


is 3


cal mol -1


This


value


is comparable


determined


capture

From the


to the organic


experimental

the M(acac)3


results


of the


compounds


for which As a


can be expected


and M(hfac)3

calculations


to apply


complexes of


given


in Table


Sc, Ti,


been


for electron


V and


4-7, for the gas-


phase


Co (NH3 ) 63+/2+


couple a


larger value


of ASao


cal mol"1


obtained


, which


was


attributed


a consequence


of the difference


in d


electron


difference


Co(acac)3

range of

electron


configuration between


in electronic


the oxidized


configuration


Co(hfac)3


20 cal mol"1


capture


results


couples


For the


acac


in the following


and reduced


is expected


and ASa may


and hfac


changes


forms.


to exist


also


complexes


same


for the


be in the


of Cr and Mn


in d electron


configuration;


Cr t2g


-t29


Mn, t2g


In each


case the


additional


electron


is accommodated


in the antibonding


set and


be in the


range of


- 20 cal mol"1


Conclusions


results


of the


calculations


presented


here demonstrate


importance of


intramolecular


entropy


changes that


occur


on electron


attachment


to coordination


complexes.


For solution-phase


redox


couples,


intramolecular


entropy


changes


are generally


smaller


than


entropy


change occurring


in the surrounding


solvent


However,


in special


cases


was


-t2g












such


as the Co(III)/(II)


changes


redox


contribute


couple,


even


couples


considered


significantly to


lons


of quite


here,


the total


small


radii.


intramolecular


entropy

In the


change


case


entropy

for the


of redox


couples


involving


large


ions


such


as Co(bipy)33+/2+


differential


solvation


effects


are expected


to be


relatively


small


probably

change.

cal mol-


be attributed


almost


For example,


and 22 cal mol


entirely to


for [
-1 K-1


Fe(bipy)3]

in water,


an intramolecular


3+/2+


entropy


[Co(bipy)3]3+/2+


respectively.


Although


extensive calculations


of the vibrational


partition


functions


cannot


carried


-20 cal mol


view of


out for these


-1 K-1


ions


difference


changes


in M-N


to the


in the ASr


stretching


lack of


o values


(and


spectroscopic data,

is understandable


presumably bending


frequencies


that


occur


for these two


couples.


Essentially no


change


vibrational


frequencies occurs


for (Fe(bipy)3 ]3++


while


frequency


change


for [Co(bipy)3]3]+2+


couple


amounts


an average


-130


insight


changes


that


gained


has enabled rough


occur


from the


calculations


estimates


for gas-phase electron


to be made


attachment


for intramolecular


for the entropy


to the


entropy

changes


transition metal


1-diketonate complexes


investigated


in this


study.


can


are

















CHAPTER


METAL-LIGAND
FOR GAS-PHASE


BOND


ENERGIES


TRANSITION METAL


AND SOLVATION


ENERGIES


TRIS(ACETYLACETONATE


COMPLEXES


AND THEIR ANIONS


Introduction


There


have been


several


attempts


to determine


average


homolytic


and heterolytic


M-0 bond energies


in M(acac)3


complexes.


most


reliable


are obtained


through a


thermochemical


cycle based


on the


enthalpy of

calorimetry.


hydrolysis


the complexes,


In the auxiliary thermochemical


obtained by using


data required


reaction


in the


cycle,


value


for the


homolytic


bond


enthalpy


of the enolic O-H bond


in acetylacetone


introduces


the greatest


uncertainty,


since no


experimental


data


is available.


From


the results of


thermal


gas-phase


charge-transfer


reactions


involving


acac


Sions


presented


here,


proton

of this


affinity


acac


bond energy.


previously


reported,


From the original


reaction


a new estimate


calorimetry


can be made


data,


better


estimates


heterolytic


bond


can


then be made


energies


for M(ac


for the average

ac)3 complexes.


e M-O


This


homolyti

s data,


combined


with


the gas-phase electron attachment


data


for the M(acac)3


complexes


and the free gas-phase


ion,


leads


to the


average


heterolytic


bond


energies


in the corresponding M(acac)3


Sions.


Several


the M(acac)3


complexes


for which


electron


attachment


data


were obtained


also exhibit


reversible


electrochemical


behavior


one electron


reduction.


From El2


data,


estimates


can be made of


single


a 1 a 4. aA a a -. A 1 a fl ante a --- I .L. t.


L -- A L --


^ _- _< _












essential for

processes at

contributions


a complete


understanding


coordinated metal

of the changes i


of the


centers.


n solvation


thermodynamics


Consideration


energies


of th


and bond


of redox

e relative

energies


that


occur


for electron


attachment


to M(acac)3


complexes


provides


overall


related


appreciation of


to the magnitude of


how ionization


a particular


potentials


M(acac)3


M+3(g)


redox


ions


are


couple.


Electron Attachment


Enerov Relationships


The general


thermochemical


cycle


in Figure


5-1 is the basis


most


of the


thermochemical


results


presented


in this


report.


The cycle


shows


the general


functions


thermochemical


for M-L bond


formation


relationships between


or solvat ion


thermodynamic


a complex


electron attachment


three


thermodynamics


physically different


(AXa)


environments


for a metal


(reactions


ion in essentially


b and


given


temperature.


A cycle of


this


type


and crude estimates of


various


thermodynamic quantities


were discussed by


Buckingham and


Sargeson


some


years


ago.


In reaction


electron


attachment


to a metal


ion M with


charge


z in the free gaseous


state,


MZ(g


electron


attachment


is to the gas-phase


complex


of charge


n in which


the metal


ion M


is equivalently


ligated by


anionic


ligands


In (c)


solvated metal


complex


is reduced


to (MLy]n-1(soln)


For the M(acac)3


complexes


considered


here,


L=acac,


= 3,


= 0.


In the


upper


part


of Figure


, labelled


the difference


for the electron


attachment


reactions


(a) and (b),


given by


AXao[MZ(g


and AX[ MLyn(g)


are thermochemically related


to the


= +3,

















































































W.>.


J












In the


part


of the cycle


labelled


II the difference


in AXa


for the


electron


attachment


reactions


AXa [(MLyn(g


and AXao[MLyLn(soln)]


thermochemically related


to the difference


between AX


solvation


the oxidized


and reduced


forms of


the complex


AXso v[MLY


AXsotv [MLy


(n-1)])


Experimental


ionization


results


of a neutral


for reaction


or electron


usually


attachment


involve


a neutral.


incorporate


the energies


for these


processes


into


thermochemical


cycles,


the values must be determined


under thermal


conditions.


Such


data


be obtained by using mass


spectrometry through


studies


of electron-


transfer


equilibrium reactions


and are often


used


to estimate


adiabatic


ionization


energies or


the electron


affinities


of polyatomic


species


(these quantities


of formation


The method


of the neutral a

d can be applied


strictly the

nd its ion at

equally well


differences between


as discussed


to reactions


the heats


in chapter


involving


positive or negative


ions,


but such


data


for metal


complexes


scarce.


Vertical


ionization


data


are more widely


available


for volatile metal


complexes


photoelectron


adiabatic


from studies of


spectroscopy

and vertical


ionization


(PES).


appearance


56,131


processes


potentials


The energy difference between


can be


relatively


small


if the


geometry

adiabatic


of the neutral


ionization


is similar to


energy


that


for ferrocene


ion.


has recently


been


example,

estimated


.69 eV by


FTICR133


(Mautner134


suggests


6.81


eV from


pulsed


high


pressure mass


spectrometry


studies),


while


vertical


IP value


obtained


from PES


6.88


Significant


differences between adiabatic


verti


cal energies


arise,


however,


when geometry


changes


upon


electron


attachment


can












7.0 eV


For metal


complexes,


therefore,


vertical


ionization


data


only


be used


in thermochemical


cycles


such


as Figure


5-1 for those


cases


where


it is known,


or can be


reasonably


assumed,


that


the geometries


the neutral


and the ion


are not too dissimilar.


It should be


noted


that


even


if the


0-0 transition


energy


(the


adiabatic energy)


can be obtained


from the


PES spectrum,


a statistical


mechanical


calculation must


be used


to derive enthalpy,

temperature. Spect


entropy,


and free


roscopic data


needed


energy


changes


for such


a given


calculations


are often


unavailable or


incomplete


for transition metal


complexes.


On the other


hand,


electron-transfer equilibrium


studies


provide data


that


can be


used


directly


in thermochemical


calculations


involving


ioni


zations


electron


attachments


near


room temperature.


Combining cas-phase electron


attachment


energi.es


with


other


thermochemical


data.


In order to


combine thermal


gas-phase


electron


attachment


energy data


for M(acac)3


complexes with


other thermochemical


data


it is useful


to know the


temperature dependence


of Ke


2-2)


since


such


data


leads


to values


of ASa


and AHa


Estimates


of AG
a


other


temperatures


can then be made.


From


the conclusions


drawn


from


chapter


concerning the magnitudes


of ASa0


for gas-phase


coordination


compounds,


a maximum


value of


= 20 cal mol'


for the


reaction


Co(acac)3(g)


- Co(acac)3


is assumed.


value


for AHa
a


at 298


K is


-7 kcal


mol"1


higher


than AG8


at 350 K (assuming


independent


of temperature).


For the other


M(acac)3


couples


where


less


change


in vibrational


and electronic


entropies occur,


ASaO


should


be smaller


Values


similar


for the


to the values


total


reported


for organic


metal-ligand heterolytic


bond


compounds.


dissociation


enthalpies


for M(acac)3


complexes


(AHhet


(M-(acac)3]


of the


first


S


can












using the


approximation AG


= AHa


(298


K) is small,


since


these


bond


enthalpies


have


values


in the range of


-600-650


kcal


(see


below)


When quoting


an average energy per


bond,


AXhet


(M-O)


error


introduced by


assuming


- AHa


is probably


kcal


cases


As discussed above,


throughout


dissertation


stationary


ectron


entropy

of AHa


convention


zero


is adopted,


to the


for monoatomic


which


free electron.


ions


at OK


apply


assigns


a heat


Under this


capacity


convention


at all temperatures,


values


since


heat


capacities


of Mz


and M(z'1)


are always


equal.


Therefore,


values


AHa M+3(g)

potential


are given by the

for the metal. T


negative


value of


stationary electron


third


ionization


convention


is adopted


to maintain


organic


consistency with


reference


the original


compounds on which


AGa values


the results


quoted


presented


for the

Ln this


dissertation


are based.


From cycle


II of Figure


5-1, AG0 M(acac)3(g)


data


can be


compared


with AGa

between t


for the


same process


solvation


free


in solution


energies


to yield


of a M(acac)3


the difference


neutral


its anion.


Values


of AGa M(acac)3(soln)


can be estimated


from electrochemical


values


for M(acac)3


AG8[M(acac)3(g)]


couples


data


(see discussion below).


at 350 K is valid at


Assuming


other temperatures


again


introduces


an approximation,


but using the


upper


limit


of -20 cal


for ASa0
a


, the error


introduced


in quoting values


AAG sov


acac)3


In the


at 298 K is again


thermochemical


used


typically


kcal


in this work


mol"1


to obtain


values


the bond


dissociation


enthalpies


for M(acac)3


and M(acac)3


complexes


value


for AHa


at 298 K for


acac"


radical


is needed.


value obtained












Homolvtic


and Heterolvtic


Bond


Enthalpies


in M(acac)ygql


Complexes


and M(acac)3


(c) Ions


The difference


total


heterolytic


or homolytic metal


-ligand bond


dissociation


enthalpies


between


any M(acac)


complex


and its


negative


ion can be obtained


from the relationships


AAHhet [M-(acac)


- AHhet


[M-(acac)3]


- AHhet[M-(acac)3


= AHa[M+3(g)]


- AHa[M(acac)3(g)]


AAHhom,[M-(acac)3


= AHho[M-(acac)3]


= AHa[M(g


- AHhmo[M-(acac)3 ]


- AHa[M(acac)3(g) ]


5-1 (b)


Values


for the


electron


attachment


energies


required


eq 5-1


given


in Table


Before deriving the


average bond


dissoc


nation


enthalpies


for the gas


-phase M(ac


ac)3 ions


by using


5-1 (a)


and 5-1


available data


for the


corresponding neutral


bond


enthalpies


critically


assessed


SInaccurate


assumptions made


in the


literature


derivations


revise the


required

published


us to generate new experimental


enthalpies


as discussed


in the


data


and thereby


following.


For M(acac)3


complexes


average


homolytic metal-oxygen bond


enthalpy,


AhoMn (M-O),


can be


found


from the


thermochemical


cycle


Figure


5-2.


The relationship between


various


thermochemi


values


is given


5-2.


AHhom


(M-O)


= 1/6


3AH (Hacac


+ 3AHvap


(Hacac)


+ 3AHhm(H-acac)


+ AHsub


- AHf[M(acac)


- AHsub([M(acac)3


- 3/2AHf[H(g)]


5-1 (


was


are











91





O
ra
0x
i-4



of
0


0 oa


C)

2 o






OD I
0 0)'


u 0) x N
0) _____ o0o__^









*mP
o+C
U a
aa




o> 0




-m +
o 0
o a. 4-- I"
U X + Ilo

Sc 0 0__ _
10









8 0
3c ^^ ) 'U


2 eJ
,C
t a)
0
-5-..







0C *s^o^
U' 0) S

0-' -.4-
3= =










)C
4-- U..












Table


5-1.


Free


M(acac1 complexes
ions an M(Qa.


Energies


of Electron Attachment


and Enthalpies


(kcal


of Electron Attachment


mol"


to Free M+3


AGa [M(acac)3


(g) ]


AHao[M+3 bg)]


AHao[M(g) ]c


-633.53


-24.9


-675.45


-713.5


-12(

-15(


-775.9


-43.0 0.5


-47 2


-38.7


-706.35


-772.0


0.5


-656


8(4.6)


-16(5)

-25(7)


aAll


values


taken


from Table


(temperature


= 350 K)


bValues
metals


given are negative of
taken from ref. 137.


CElectron affi]
in parenthesis


na


ity data
is the u


the third
Conversion


for atomic metal


uncertainty


ionization


factor


taken


in the last


potentials


= 23.065


from ref.


Kcal


138.


of the
mol"


Number


figures)


v












between


AHho0(M-O)


and the


average


heterolytic metal


oxygen


bond


enthalpy


AHhet


given


5-3.


M-O)


The summation


- -
6


term


M-O) +


^iIP(M)
i-i


5-3 is the sum of


+3AHa


first


(acac


three


ionization


potentials


for the metal M.


Values


for AHf0


for M(acac)3


complexes


first


transition metal


series


are available


in the


literature


from


results


results


of Wood


of reaction


and Jones


using


calorimetry.


bomb calorimetry139


140-143


Reaction


from


calorimetry


considered


to be the more


reliable method


for M(acac)3


compounds


144,141a


this


technique


has been applied


to M(acac)


complexes


of interest


here


for M


= Cr, Mn,


Fe and Co.


141,142


Reaction


calorimetry


been


used by


Ribeiro


Da Silva


and co-workers


to determine values


of AHf0


AHho ( M-O


technique


for other tris


B-diketonate


to transition metal


complexes,


B-diketonates


application


has been


reviewed.


Their work

AHhno(M-O)


included


derived


a reappraisal


from the original


of of the


reaction


values


of AHf0


calorimetry


studies,


values


have


been


revised


here


using the


latest


values


of the


auxiliary thermo


chemical


data


required


for their


determination.


values


that


introduce


the greatest


uncertainty


in derived


bond


phase


enthalpies

homolytic


for the M(acac)3


bond


dissociation


complexes


enthalpy


are


values


of the O-H


of the gas-


bond


enol


form of


acetylacetone


(AHh" (H-acac)


eq 5-2)


and the enthalpy


sublimation


of the M(


acac)3


complex


Values


for AHsub0[M


acac)3]


difficult

volatility


to measure


such


prec


isely


as M(acac)3


for compounds


complexes.


of relatively


For example


values


for AHsub


fnr Crtacaci


noted


.1.. I r~ r1f~s. r rIlrrl n nfl rr~ I r*~r1 '1 aot4


--- -


CT !'A


I--- -


- I


are


(M-O


AHhet


16A hom


n1 Cob


I


I |


q


r nn u r-rn nTT nar^












earlier work


was recognized


in the reappraisal


Ribiero


Da Silva


co-workers.


From


a review of


the results


available


in the


literature,


values


of AH [M(acac)3]


chosen by these workers were


in the


range


of -28-33


kcal


1 The


same


values


were


used


in this


report


are given


in Table


5-2 along with


the other


auxiliary


data


used


in Figure


5-2.


No experimental


values


have


been available


for the


value of


AHho(H-acac),


and values


used


previously


have been


estimated.


difficulty


assess


ing the contributions


to the relative


stability


acetylacetone


due to


intramolecular


hydrogen bonding


in the


enol


form


the effects of


electronic delocalization


in the


acetylacetonate


radical


led to estimated


values


ranging


from 87-110


kcal


-1 139,1I


A value of


AHho0 (H-acac)


can be obtained


from the


gas-phase


proton


affinity


AHpA)


acac


-,146
9


acac"


and the


ioni


zation


potential


H atom.


The relationship


given by


AHhon (H-acac)


= AHpA(acac


- IP(H(g))


- AHao(acac-)


Substituting the


available


data


from the


literature


and AHa


acac"


determined


in this


report


(Table


5-2)


into eq


yields


a value


AHho(H-acac)


of 90 + 5


kcal mol


The new value


for the


AHho ( H-acac


combined


with


reaction


calorimetry


data


leads


to new values


of AHh,o(M-o)


AHhet


(M-O)


the M(


acac)


complexes


of Cr, Mn,


Fe and Co


, and these


values


are


given


in Table


5-3.


Also given


in Table


are the values


AAHhet


(acac)


obtained


from eq


the data


Tabli


resulting


AHhet


(M-O)


and AHh0 (M-O)


values


from eqs


r 4-b


af~


U -. n


S


- .


5 *% n -S a.an 1 nn~ m.. 1 a C.


5-1 (


A


ik *


[M-


C- -1


Ik J


s *". i




Full Text

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THERMODYNAMIC ASPECTS OF GAS-PHASE ELECTRON ATTACHMENT
TO TRANSITION METAL TRIS(BETA-DIKETONATE) COMPLEXES
By
PAUL SHARPE
*â– * tm>
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL
FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1990

ACKNOWLEDGMENTS
First I must thank my research director Dr. David E. Richardson
for his understanding, guidance and support throughout my graduate
career. Dr. John R. Eyler and Dr. Cliff Watson also deserve
considerable recognition for their many contributions and useful
discussions, especially on help with the instrumentation.
No dissertation would be complete without acknowledging all the
friends and loved-ones for their support. Foremost in my mind in this
regard is Stephanie Weinstock, whose love and understanding have been a
constant source of encouragement over the last two years. Also, I would
like to thank my mother, and my late father whom I know would have been
proud.
Finally, I will always remember my colleagues in Graduate School
at the University of Florida especially Matt, Casey, Mike and T.M. who
greatly enhanced the enjoyment of graduate school at Florida.
ii

TABLE OF CONTENTS
page
ACKNOWLEDGMENTS ii
ABSTRACT v
CHAPTERS
1 INTRODUCTION 1
Overview of Research 1
Introduction to Metal B-Diketonate Complexes 8
Properties and Applications of Metal B-Diketonates 12
Description of the FTICR Technique 18
2 EXPERIMENTAL PROCEDURES AND RESULTS 23
Preparation of Tris(hexafluoroacetylacetonate)
Complexes 23
Preparation of Tris (acetylacetonate) Complexes 25
Preparation of Ruthenium Tris(B-Diketonates) 25
Organic Compounds 26
Electron Attachment Studies 26
Gas-Phase Spectrophotometry of Cr(hfac)3 37
3 TERMINOLOGY AND CONVENTIONS USED IN GAS-PHASE
ION THERMOCHEMISTRY 38
Introduction 38
Electron Affinities and Adiabatic Ionization
Potentials 39
Stationary and Thermal Electron Conventions 40
4 INTRAMOLECULAR ENTROPY CHANGES FOR REDOX COUPLES
INVOLVING COMPLEX METAL IONS 48
Introduction 48
Statistical Mechanics Applied to the Determination
of Gas-Phase Intramolecular Entropy Changes for
Redox Couples Involving Complex Metal Ions 51
Comparison of Solution-Phase and Gas-Phase Entropy
Changes for Some Redox Couples Involving Octahedral
Metal Complexes 72
The Relationship Between The Free Energy and Enthalpy
of Gas-Phase Electron Attachment to M(acac)3 and
M(hfac)3 Complexes 80
Conclusions 82
iii

5 METAL-LIGAND BOND ENERGIES AND SOLVATION ENERGIES FOR
GAS-PHASE TRANSITION METAL TRIS(ACETYLACETONATE)
COMPLEXES AND THEIR ANIONS 84
Introduction 84
Electron Attachment Energy Relationships 85
Homolytic and Heterolytic M-O Bond Enthalpies in
M(acac),(g) Complexes and M(acac)3'(g) Ions 90
Relative Solvation Energies of M(acac)3(g)
and M(acac)3'(g) 99
Relative Solvation Energies of Ru(tfac)3(g) and
Ru(hfac)3 and Their Negative Ions 108
Conclusions Ill
6 INTERPRETATION OF THE TRENDS ON THE ELECTRON ATTACHMENT
FREE ENERGIES OF THE TRIS(ACETYLACETONATE) AND
TRIS(HEXAFLUOROACETYLACETONATE) COMPLEXES OF THE
METALS Ti-Co USING THE SIMPLE LIGAND FIELD MODEL 113
Introduction 113
Thermochemical Relationships and Periodic Trends 114
Conclusions 128
REFERENCES 130
BIOGRAPHICAL SKETCH 139
iv

Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
THERMODYNAMIC ASPECTS OF GAS-PHASE ELECTRON ATTACHMENT
TO TRANSITION METAL TRIS(BETA-DIKETONATE) COMPLEXES
By
Paul Sharpe
August 1990
Chairman: David E. Richardson, Ph.D.
Major Department: Chemistry
Estimations of the free energies of gas-phase electron attachment
to several transition metal tris(B-diketonate) complexes at 350 K are
reported. The compounds studied are the tris(acetylacetonate) complexes
(M(acac)3) and the tris(hexafluoroacetylacetonate) complexes (M(hfac)3)
of the series of first row transition metals M = Ga - Co. In addition,
data for the ruthenium complexes Ru(acac)3, Ru(tfac)3 and Ru(hfac)3 are
reported, where tfac is trifluoroacetylacetonate. This work represents
the first reliable estimations of thermal gas-phase electron attachment
energies for a class of coordination compounds.
Electron attachment free energies for the complexes were obtained
by using Fourier transform ion cyclotron resonance mass spectrometry
(FTICR) to monitor charge-transfer bracketing and equilibrium reactions
involving parent negative ions trapped in a mixture of two gases. The
gas mixture consisted of a metal complex and an organic reference
compound, for which the electron attachment free energy is established.
Theoretical intramolecular entropy changes for some redox couples
involving coordination complex ions are estimated and compared, where
possible, to experimental solution-phase results in order to gain an
appreciation of the entropy change and enthalpy change for gas-phase
electron attachment to the coordination compounds in the present study.
v

The electron attachment energy data are combined with other
thermochemical data in energy cycles that lead to estimations of the
changes in heterolytic M-O bond enthalpies and solvation free energies.
The observation of charge-transfer bracketing reactions involving
acetylacetonate anions led to the determination of the heterolytic and
homolytic M-O bond enthalpies for M(acac)3 neutrals and their anions.
Published estimations of the absolute potential of the standard hydrogen
electrode led to estimations of the free energy for solution-phase
electron attachment to the complexes in several solvents. For
Ru(acac)3, the single ion solvation free energy is estimated, and the
result is discussed in comparison to a similar estimation based on a
dielectric continuum theoretical model.
The results of this investigation serve to illustrate the relative
importance of changes in bond energies and solvation energies that
determine the magnitude of redox couples involving reduction of tris(13-
diketonate) complexes.
vi

CHAPTER 1
INTRODUCTION
Overview of Research
Many methods have been used for the determination of gas-phase
electron attachment energies of atoms and molecules. These methods can
be categorized into theoretical, semiempirical and experimental, and
these various approaches have been reviewed.1 Although some of the
published data on gas-phase electron attachment energies has been
determined from solution-phase studies such as polarography and reaction
calorimetry, the majority of the published work to date stems from the
experimental methods that study gas-phase negative ions directly. These
methods were actively developed during the early 1970s. Gas-phase
methods rely on a ready source of ions, which is by far most easily
accomplished by the ionization of a gas. Hence, the majority of
determinations have been performed on ions formed from volatile
precursors. In the case of metal-containing compounds, studies of
negative ions have been restricted to those formed from metal halides,
especially hexafluorides, oxyhalides, and carbonyls.2 These compounds
are all gases or volatile liquids or solids. In particular, transition
metal hexafluorides have received a great deal of attention. It has
long been known that these compounds are the most highly oxidizing
compounds known, typically having electron affinities in the range of
“ 3 eV to 10 eV.
The majority of experimental methods involving gas-phase negative
ions that have been used to determine the electron attachment energies
of metal complexes can be classified as threshold methods. In threshold
methods electron attachment energies are inferred from the minimum
1

2
energy of an impinging particle that causes the formation or breakdown
of a negative ion. In the atom impact method, beams of energy selected
neutral alkali atoms are collided with a neutral target gas. The
translational energy dependence of the alkali atom beam is monitored as
a function of the relative cross section for the formation of the parent
anion of the target molecules. Using this method, Compton and co¬
workers have provided estimates for the electron affinities of MoF6,
ReF6, UF6, UF5, SeF6, TeF6 and WF6.3,4 A related method involves
colliding negative ions into a target gas. The translational energy of
the negative ions is varied and the threshold energy for the onset of an
endothermic electron-transfer reaction is detected by the observation of
the formation of product ions. The ion-molecule reaction may be simple
charge-transfer or may be accompanied by atom transfer, such as proton
transfer. The enthalpy of formation of the anion of interest can be
determined from the enthalpies of formation of all other species
involved in the reaction, combined with the threshold value of the
translational energy of the negative ion beam. Although the energy of
the atomic and negative ion beams in these methods can be controlled to
within a range of energy of ± 0.1 eV, there are several problems
encountered in obtaining acurate electron attachment energies. Most
prominent are the sensitivity of the threshold energy to the thermal
distribution of the translational energies of the target gas, the
weakness of the signal around the threshold energy and the lack of
information on the initial and final states of the neutral molecules and
product ions. Due to the inherent problems these methods have produced
results for electron affinity values for transition metal hexafluorides
that are in considerable disagreement. For example, the range of
electron affinity values reported for tungsten hexafluoride extends from
2.75 - 5.5 eV.5'6
More accurate determinations are possible with photodetachment and
photoelectron spectroscopy methods. Both of these methods are based on

3
the detachment of an electron from a negative ion, according to eq 1-1,
by using photons of known energy generated by a laser, or light source
with monochromator.
AB' + hv = AB + e' 1-1
Photodetachment methods use a variable frequency laser to detach the
electron from the negative ion AB’. The threshold energy can be
obtained by using a variety of physical methods that detect either the
detached electrons or the formation of neutral molecules from the anions
as a function of photon flux and wavelength. The interaction of the
negative ions with the photon flux has been accomplished in crossed
photon-molecular beam experiments, drift tubes and in ion traps.7
In photoelectron spectroscopy,1 the frequency of the photon source
is fixed and the energy spectrum of the emitted electrons is recorded.
For simple molecular anions, composed of a few atoms, the energy
spectrum can be resolved into the vibrational transitions accompanying
the detachment process. Determining the energy of the ejected electrons
from the ground vibrational states of the neutral and the anion leads to
very accurate determinations of the electron affinity of molecules.
Using the photoelectron spectroscopy method, Lineberger and co-workers
have determined the electron affinities of several carbonyl complexes of
Fe and Ni, which are in the range of 0.6 - 2.4 eV.8,9 A limitation of
extending the technique to high electron affinity compounds such as
volatile metal hexafluorides is that although it may be possible to
identify the energy transitions in the spectra, producing a light source
of the required wavelength and flux is impractical for compounds of such
high electron affinities.
The picture that emerges is that due to the volatility and/or high
electron affinity restrictions imposed by metal containing compounds,
few reliable data are currently available.

4
Since about 1982, techniques in mass spectrometry that are capable
of following the time dependence of ion-molecule reactions have been
used to determine the electron attachment energies of polyatomic
molecules. In these methods the equilibrium constant for a gas-phase
charge-transfer reaction involving two neutral reactants and their
parent negative ions is measured. These methods have therefore been
described as equilibrium methods. The techniques in mass spectrometry
that have been used for this purpose are pulsed high pressure mass
spectrometry (PHPMS)10-15 and ion cyclotron resonance mass spectrometry
(ICR).16-19 Electron attachment energies for many different organic
compounds have been reported, and values are in the range of 0.5 - 3.2
eV. The types of new compounds studied is still expanding and many more
determinations are reported each year. One of the advantages of the
equilibrium method over threshold methods for determining electron
attachment energies is that the moleular ions formed after ionization
are cooled to the same temperature as the neutral molecules from which
they are formed, usually by a thermalizing bath gas. Electron
attachment energies are therefore obtained at a definite temperature and
may be combined with other thermochemical data, especially electron
attachment energies in condensed-phases. For example, many of the
organic compounds studied exhibit reversible electrochemical behavior
and this has led to estimates of the change in solvation energy for
solution phase reduction of these compounds.14,15,20
A relatively recent technique in mass spectrometry that is also
capable of monitoring the time dependence of ion-molecule reactions is
the versatile and powerful Fourier transform ion cyclotron resonance
mass spectrometry (FTICR). An important difference between FTICR and
other techniques in mass spectrometry is that only very low operating
pressures of reactants are required. This feature makes FTICR
particularly suitable for the study of low-volatility compounds. Hence,
FTICR has been exploited in the study of gas-phase ion-molecule

5
reactions of metal containing compounds.21'43 Much of the published
research considers ion-molecule processes involving metal containing
ions (mostly derived from organometallic precursors) or bare metal ions
pi _
(produced by techniques such as laser vaporization of metal targets).
34 The bulk of this work has centered on the reactions of bare metal
ions or highly coordinatively unsaturated metal ions with C-H and C-C
bonds.21'34 Relatively little attention has been given, however, to
coordinatively saturated metal complexes with non-carbon donor ligands,
such as coordination complexes.
There were two principal objectives of the present work. The
first was to determine the free energies of thermal electron attachment
for a series of coordination complexes by using the FTICR technique,
thereby extending the established charge-transfer equilibrium method for
the determination of free energies of electron attachment to
coordination complexes. The compounds studied in the present work were
the tris(acetylacetonate) (M(acac)3) and tris(hexafluoroacetylacetonate)
(M(hfac)3) complexes of the series of metals M = Sc - Co and Ga. The
complexes Ru(acac)3, Ru(hfac)3 and Ru(tfac)3 were also included (where
tfac = trifluoroacetylacetonate). These complexes are pseudo-octahedral
tris chelate coordination complexes in which the ligands bind to metal
centers with oxygen atom donors. Estimates of the free energies of
electron attachment for these complexes were obtained in the present
work, and this represents the first reliable determination of the gas-
phase electron attachment energies of coordination complexes under
thermal conditions.
The second objective was to determine the changes in average
heterolytic metal-oxygen (M-O) bond energies that occur during gas-phase
electron attachment to the fi-diketonate complexes. Also, for the
complexes that exhibit reversible one-electron electrochemical reduction
in solution, determine the changes in solvation energies that contribute
to the magnitude of the reduction potential. These energies were

6
obtained by incorporating the electron attachment free energy data for
the complexes into energy cycles35 that relate the energy for this
process to the energy for electron attachment to the free metal ions and
the coordinated ions in solution. To obtain the change in average M-O
heterolytic bond enthalpies a value of the entropy change for electron
attachment to the complex is required.
Estimates of entropies could be obtained, in principle, by
determining the temperature dependence of the equilibrium constants for
the gas-phase charge transfer reactions. There is no provision on the
FTICR instrument used in this study to determine the temperature
dependence of ion-molecule reactions. Therefore, statistical mechanics
was used to attempt to provide estimates of entropy changes for gas-
phase electron attachment to coordination compounds. The results of the
calculations reported in this study have provided insights into the
magnitudes of entropy changes for electron attachment processes
involving coordination complexes, both in the gas-phase and in solution,
and have enabled estimates to be made for the change in heterolytic M-0
bond energies. Data of this type are scarce for metal complexes. The
M(H20)63+ and M(H20)62+ ions, where M are first transition series metals,
represent one of the few series of complex ions for which metal-ligand
bond energies and solvation energies are known for both ions that form
the redox couple. Generally, even less is known of the thermodynamics
of redox processes at metal centers involving negative ions. The data
obtained for the fi-diketonate complexes in the present work therefore
broaden the present understanding of the thermodynamics of redox
processes that occur at transition metal centers in different
coordination environments.
Several attempts have been made to determine the average homolytic
and heterolytic M-0 bond dissociation enthalpies in M(acac)3 complexes.
In the auxiliary thermochemical data required in the cycles used to
obtain these values, the value for the homolytic bond dissociation

7
enthalpy of the enolic O-H bond in acetylacetone introduces the greatest
uncertainty since no experimental data are available. From the results
of thermal gas-phase charge-transfer reactions involving acac’ ions,
presented in the present work, an improved estimate is made for the
enolic O-H bond enthalpy. From the original reaction calorimetry data
improved estimates are made for the average M-0 homolytic and
heterolytic bond dissociation enthalpies for M(acac)3 complexes. This
data, when combined with the gas-phase electron attachment energy data
for the M(acac)j complexes, has allowed the average heterolytic and
homolytic bond dissociation enthalpies for the corresponding gas-phase
M(acac)j' ions to be determined.
It has been shown for M(H20 ) 63+/2+ redox couples of the first
transition metal series ions that the trend in the magnitudes of the
reduction potentials for these couples can be related quite successfully
to the trend in the electron attachment energies of the free M+3 ions
(the negative value of the third ionization potential of M(g)) by
correcting the reduction potentials for the difference between the
heterolytic M-O bond enthalpies in the oxidized and reduced form of each
redox couple.35*37 Although the difference in absolute magnitudes of
electron attachment energies between M+3 ions in the gas-phase and in
solution can only be accouted for by additionally considering solvation
energies, nephelauxetic effects in the complexed ions and the absolute
potential of the electrochemical reference electrode used, the periodic
variance of the sums of these quantities is generally small enough to be
neglected when compared to the difference in heterolytic bond energies.
The trend in the difference between metal-ligand heterolytic bond
energies between the ions that form redox couples can be estimated from
the appropriate spectroscopic data, when used with the crystal field"
model. For M(H20)63+72+ ions, differences in ligand field stabilization
energies have been derived spectroscopically and have been used to
"correct" the values of the reduction potentials to generate the trend

8
line for the electron attachment energies of the free ions. In this
way, a simple explanation is provided for the trends in the reduction
potentials. The trend in the gas-phase electron attachment energies for
the M(acac)j complexes in the present work is explained by using a
similar approach to that taken for the M(H20 ) 63+/2+ couples.
Introduction to Metal B-Diketonate Complexes
The transition metal complexes investigated in the present work
belong to the general class of metal B-diketonates.38,39 There are a
great many B-diketone ligands that coordinate to metals. The general
structure of B-diketones is shown in Figure 1-1. The most common
ligands have R1 and R2 = alkyl, perfluoroalkyl and aryl groups, and R3 =
hydrogen, but several other ligands have been reported in which R3 is
also alkyl or aryl.
Rj H
\ /
C
0 0
Keto Form
R,
R3
I
c
/ 0%
R,
0
X
I
0
Enol Forms
R3
i
c
X p \
I
0
\
Figure 1-1. Structure of B-diketones in keto and enol forms.
Figure 1-1 illustrates the the keto-enol tautomerism that exists
in many B-diketones. The hydrogen atom at the B ring carbon atom is
activated by the adjacent C=0 groups and a conjugate system can arise
from the prototropic shift. These tautomers exist in equilibrium with
each other, and structurally they possess a cis configuration and a syn

9
R1
R2
R3
Ligand
Abbrev
ch3
ch3
H
Acetylacetonate
acac
CHj
cf3
H
Trifluoroacetylacetonate
tf ac
cf3
cf3
H
Hexafluoroacetylacetonate
hf ac
t-butyl
t-butyl
H
Dipivaloylmethanate
dpm
phenyl
ch3
H
Benzoylacetylacetonate
bzac
Figure 1-2.
Structure
and
nomenclature of fi-diketonate
ligands.

10
(cisoid) conformation. The proportion of the enol tautomers generally
increases when an electron withdrawing group such as a halogen atom is
present as R3. The enolization also increases when the ligands are
fluorinated or contain an aromatic ring. Substitution by a bulky group
(e.g. alkyl) at the ring a or y carbon atoms causes steric hindrance
between Rj and R1 (or R2), particularly in the enol tautomer, and this
together with the inductive effects of the alkyl groups may
significantly reduce the proportion of the enol tautomer at equilibrium.
Since complexation to a metal is believed to occur through the enol form
of the ligand, attempts to obtain metal complexes of these ligands often
result in poor yields.
The complexes investigated in the present work are tris-chelate
transition metal complexes of the ligands hfac, tfac and acac. The
structures of the coordinated ligands are given in Figure 1-2. The
structure of the complexes themselves are shown in Figure 1-3, which
shows the two optical isomers that exist in tris B-diketonate complexes.
Figure 1-3. Structure and optical isomers of tris(B-diketonate)
complexes.

11
Table 1-1. Structural Details of Metal Tris (fl-Diketonates).
Average Average
O-M-O Bite M-0 Bond
Complex
Angle
Length
V(acac)3(a)a
88.0°
1.979
V(acac)3(J3)a
87.3°
1.982
Cr(acac)3b
91.1°
1.952
Mn(acac)3c
97.2°
1.901
Fe(acac)3d
87.1°
1.992
Co(acac)3e
97.3°
1.898
Co(acac)"
(Bu4N+ salt)f
91.5°
1.981
Ru (acac )39
94.0°
2.000
Cr(hfac)3h
87.0°
1.987
Fe(hfac)3'
87.0°
1.999
aData taken from
ref. 40.
hoata taken from
ref. 41.
cData taken from
ref. 42.
dData taken from
ref. 43.
eData taken from
ref. 44.
fData taken from
ref. 45.
9Data taken from
ref. 46.
hData taken from
ref. 47.
'Data taken from
ref. 48.

12
For symmetrical ligands (R1 and R2 in Figure 1-2 are the same),
two optical isomers are possible (Figure 1-3). The d and 1 optical
isomers of Cr(hfac)3 have been isolatated by gas-chromatographic
techniques by using an optically active support.1*8 For unsymmetrical
ligands (R1 and R2 in Figure 1-2 are not the same) each optical isomer
can exist in a cis or trans conformation. It has been found by using a
gas-chromatograph equipped with an electron capture dectector that
Cr(hfac)3 undergoes dynamic cis-trans intramolecular isomerism in the
gas-phase.49 Tris(B-diketonate) transition metal complexes of
unsymmetrical ligands have received considerable attention regarding
investigations of the mechanisms that have been proposed for
intramolecular structural isomerism in tris-chelate complexes.50'52 For
several of the tris-chelate metal complexes studied in this report,
X-ray crystal structures or gas-phase electron diffraction structures
are available. The "bite" angle of the ligands and the M-O bond lengths
obtained from these investigations are presented in Table 1-1. The
"bite” angle of the oxygen donor atoms is in all cases is quite close to
90°, which gives a pseudo-octahedral arrangement about the central metal
atom of O donor atoms.
Properties and Applications of Metal B-Diketonates
In this section some background is given of the chemical and
physical properties and applications of transition metal B-diketonates.
The emphasis is on the M(acac)3, M(tfac)3 and M(hfac)3 complexes of the
first transition metal series, which are the subject of the present
study, although other complexes are included. Much of the relevant
material which should appear in this section is discussed or referenced
in later chapters and is not presented here.

13
Rather, this section deals with the more interesting and relevant
miscellaneous literature on transition metal B-diketonates that may
serve to acquaint the reader with these compounds.
The physical and chemical properties of transition metal
B-diketonates have generated a great deal of research interest since
they were first synthesized in the year 1887. The interest in these
compounds stems not only from their spectroscopic and structural
properties as coordination complexes, but also from their remarkable
physical properties. Many metal B-diketonates are volatile, which led
Morgan and Moss in the year 1914 to describe B-diketones as the ligands
that "gave wings to metals”.53 The factors that determine the
volatility of metal B-diketonates have been discussed.31 Generally, for
octahedral complexes, an increasing amount of flúorination in the ligand
leads to greater volatility. Hence, for the complexes studied in the
present work, the order of increasing volatility is M(acac)3 < M(tfac)3
< M(hfac)3. The M(tfac)3 complexes are usually only marginally more
volatile than M(acac)3 due to the dipole moments present in the cis and
trans forms of M(tfac)3 complexes.
The volatility of transition metal B-diketonates has enabled them
to be studied by a variety of physical methods that are not readily
applied to ligated metal centers that exist as ions. The vapor-phase
He(I) photoelectron (PE) spectra of M(hfac)3 and M(acac)3 complexes have
been reported.54,55 The spectra were interpreted in terms of elementary
molecular orbital theory, which yielded information concerning the
details of the metal-ligand bonding, and in the case of transition metal
complexes, information about the the relative energies of the metal d
and ligand orbitals.
Some interesting and important work has recently been reported on
the use of metal B-diketonates in the field of organometallic chemical
vapor deposition (OMCVD) in the formation of thin film high temperature
superconductors.56'60 In contrast to physical vapor deposition, the

14
method does not require high vacuum and accordingly has the advantage of
relative ease for large scale application with the possibility of
coating complicated shapes. Thin films of superconducting YBa2Cu307
have been prepared by a process that involves thermal decomposition of a
flow of a vapor mixture of fi-diketonate precursors of Y, Cu and Ba in
argon. There are several complexes of yttrium and copper that are
sufficiently volatile and thermally stable to be used for this purpose.
These include Y(dpm)3 Cu(acac)2 and Cu(dpm)2. Barium complexes are less
thermally stable and decomposition has been reported under the
experimental conditions. The most success in this respect has been
obtained with Ba(fod)2, where fod = 2,2 dimethyl-6,6,7,7,8,8,8-
heptafluoro 3,5 octadionate. The B-diketonate precursors are
volatilized in seperate sources and their flow rates are carefully
controlled to give the desired stoichiometric ratio. Oxygen is added to
the gas mixture before it reaches a high temperature reactor containing
the substrate onto which the superconducting layer is to be deposited.
Water vapor has been added to the oxygen flow to aid in the decompostion
of the complexes by hydrolysis. Substrates used so far have been
SrTiOj, A1203 and yttria stabilized zircona (YSZ), and the deposited
films are usually 5-10 pm thick. After the decomposition period, a
variety of annealing processes have been used (depending on the
B-diketonate precursors used) to convert the initially deposited layer
into superconducting YBa2Cu307. By this method, films of good
compositional and dimensional uniformity are produced. A similar method
has been used to produce thin superconducting films of the Tl-Ba-Ca-Cu-O
type.57 These thin-film superconductors have critical temperatures in
the range of 90-120 K with the onset of zero resistance at 65-100 K.
The metal-ligand bond energy data of the type obtained in the present
work may be useful in these investigations.

15
The volatility of metal fi-diketonates has allowed several
investigations of their gas-phase positive and negative ions by using
mass spectrometry. Much of the work with positive ions has concerned
the determination of appearance potentials and mechanisms of
fragmentation subsequent to electron impact (El) ionization.63 Some
interesting work has been reported by Pierce and co-workers64 in an
investigation of the secondary ion mass spectrometry (SIMS) and laser
desorption (LD) of solid samples of transition metal /3-diketonates. One
of the aims of the study was to compare the ionic species formed by
conventional El ionization to to those formed from SIMS and LD. The
SIMS spectra revealed catonization of intact neutral M(acac)3 complexes
by ionic fragments produced in the plasma, as well as the ionic
fragments themselves. Ions of masses corresponding to the following
stoichiometries were observed M(acac)+, M(acac)2+, M2(acac)3+ and
M2(acac)^+. These species had also been observed in a study of M(acac)3
complexes using high pressure mass spectrometry.65 Catonization of
neutral M(acac)3 by Na+, Ag+ and NH^+ was also found to occur when the
chlorides of these cations were mixed with the solid sample of metal B-
diketonate. SIMS spectra of mixed samples of M(acac)3 complexes of two
different metals produced mixed metal clusters of the same general
formula. When certain mixtures of a metal J3-diketonate, a chloride of a
different transiton metal and a cationizing agent were vaporized, ligand
exchange was found to occur. For example, a mixture of Fe(acac)3, CrCl3
and NH^Cl produced Cr(acac)+, Cr(acac)2+, Fe(acac)+, Fe(acac)2+ and
[Fe(acac)-CH3]+. For other mixtures no ligand exchange fragments were
detected. The spectra of laser desorbed samples produced many of the
same fragment ions observed in the SIMS experiments. Interestingly,
during the course of the present work, ligand exchange has been observed
in gas-phase ion-molecule reactions involving negative ions formed from
mixtures of M(acac)3 and M(hfac)3 complexes of various metal and ligand
combinations. However, for complexes of the metals Cr and Ru, ligand

16
exchange was found not to occur. To probe the structure of the
bimetallic clusters, Pierce and co-workers used collisional dissociation
to observe the pathways for fragmentation. The resulting spectra
indicated that the cluster ions could not be considered simply as metal
cations. Rather, a stable structure involving metal atoms was invoked
with possible metal-metal bonding.
Reports on the negative ion mass spectra of metal fi-diketonate
complexes have focused largely on M(hfac)3 complexes due to their high
volatility and very large cross sections for electron capture. The
thrust of the work has been to determine the fragmentation pathways for
the parent ions following 70 eV El ionization.66'71 The possibility of
using negative ion mass spectra of some metal B-diketonates as an
analytical technique in the field of ultra trace metal analysis has been
investigated.67 Some results of previous investigations of negative
ions formed from metal fi-diketonate precursors are discussed in the
experimental section of this dissertation, in comparison to the results
obtained in this work.
A large number of metal tris(fi-diketonate) complexes exhibit
reversible electrochemical behavior, especially those containing the
metals Fe, Ru and Cr. There are numerous reports on the effect of the
ligand R substituents (Figure 1-2) on experimentally observed E1/2
values for electrochemical reduction of these complexes.72-76,159-164 substituent effects are quite pronounced. For example, the E^2 values
reported for Ru(dpm)3 and Ru(hfac)3 differ by 1.84 V in
dimethylformamide.76 For series of tris(B-diketonate) complexes of the
same metal, the trends in reduction potentials correlate predictably
with the electron releasing or withdrawing nature of the ligand ring
substituents. Thus, the order of ease of reduction for comlexes of Ru
and Cr is M(dpm)3 < M(acac)3 < M(tfac)3 < M(hfac)3. The delocalized n
system in that extends over the metal center and the ligand backbone
atoms in metal fl-diketonates has been described as possessing "quasi-

17
aromatic" character. It has been shown that there is a strong
correlation between the trends in E1/2 values for the reduction of a
series of tris(fi-diketonate) complexes of the same metal and Hammett a
parameters that have been derived from observations of the effect of
ring substituents on the thermodynamics and kinetics involving reactions
of organic aromatic compounds. Interestingly, for complexes of varying
R1 and R2 with R3 = H (Figure 1-2), there is generally a closer
correlation between E1/2 potentials and a para parameters than meta
parameters despite the meta position, with respect to the metal center,
of the carbon atom that bears the ring substituent.72 However, since
the oxygen donor atoms in the ligand are para to the substituted ring
carbon atoms, the phenomenon has been attributed to the distribution of
electron density at the oxygen atoms. From this standpoint the value of
the E^2 values can be explained in terms of ligand field theory by
considering the varying magnitude of the spherical component of the
ligand field produced by the oxygen donor atoms.
The quasi-aromatic nature of coordinated fi-diketonate ligands is
manifest by the occurence of electrophillic substitution reactions in
metal B-diketonate complexes.39 These reactions produce complexes that
are not easily formed by normal reaction routes. Substitution occurs at
the B carbon atom of the ligand (Figure 1-1) with a variety of
electrophiles. The wide variety of reactions can be classified into
halogenation, nitration, diazotization, thiocyanation, acetylation and
formylation. The reaction conditions must be chosen so that the acid
labile B-diketonate rings are not degraded. The most widely studied
complexes are therefore those of chromium(III), cobalt(III) and
ruthenium(III), which are not hydrolyzed in acid solution.

18
Description of the FTICR Technique
Production, trapping, and mass analysis of ions
In 1974 Marshall and Comisarow77 developed a method of applying
the Fourier transform technique to the analysis of the masses and
relative abundances of ions trapped in an ion cyclotron cell. The
simultaneous detection of many ions over a wide mass range circumvented
many of the limitations of the original scanning ion cyclotron resonance
mass spectrometry (ICR) technique. Since then, the Fourier transform
method, known as Fourier transform ion cyclotron resonance mass
spectrometry (FTICR), has developed into a powerful and versatile
technique in mass spectrometry.78
The FTICR technique is based on the classical motion of ions
described by elementary laws of electromagnetism. The magnetic force
(Lorentz force, F = q(VxB) ) acting on a particle of mass M, charge q,
and initial velocity V in a field of magnetic induction B causes it to
follow a helical path Figure 1-4. The constrained circular motion has a
frequency in Hz given by vc = qB/27rM. This frequency is the cyclotron
frequency and falls in the range of radio wave frequencies (0.01 - 2.00
MHz) for magnetic fields on the order of 1 tesla. To prevent ions from
travelling along the helical path and being lost, ions are produced
between two trapping plates perpendicular to the magnetic field. These
plates are maintained at a repulsive potential (typically +1 or -1 volt
for positive and negative ions, respectively), and the ions thereby are
held in a defined region between the two plates.
Excitation and detection of the trapped ions require two additional
sets of plates (transmit and receive plates) lying along the axis of the
magnetic field between the trapping plates, so the heart of the FTICR is
a box shaped cell of 6 plates. Cells are typically cubic7^ with each
plate of approx 1 square inch (Figure 1-5). The cell is mounted in a
high vacuum chamber in a strong magnetic field (the Nicolet FTICR-1000

19
Figure 1-4. Ions with initial velocity V are constrained to a helical
path along the axis of the magnetic field.

20
electron trapping
collector plate
Figure 1-5. Cubic analysis cell of the FTICR.

21
used in the present study has a 2 tesla superconducting magnet). Ions
can be formed in the cell from the low background pressure of an
admitted sample by an ionizing electron beam passing through small holes
in the trapping plates or by photoionization via irradiation through
semi-transparent grids in one or more plates. Application of an
external oscillating electric field across the transmit plates at the
characteristic cyclotron frequency of an ion causes ions of that mass in
the cell to move into resonance with the applied field and spiral out to
orbits of larger radius. The kinetic energy of the ion is given by
Ek = 27t£ Mvc‘ r , where r is the radius of the orbit. As the ions move
into resonance with the applied electric field their motion is shifted
from having a random distribution of phases to that of all
simultaneously moving in phase with the applied field as a "packet" of
ions. If the applied field is turned off or moves out of phase with the
ions, the ion packet persists long enough to induce an image current in
the detect plates80 before collisions with neutral molecules restore the
initial random distribution of phases. The induced image current at the
cyclotron frequency of the ion packet contains information in the time
domain about the frequency (mass) of the ion, and the intensity of the
signal produced is dependent on the ion population.
In order to simultaneously detect the masses and populations of
many different ions present in the cell, a fast radio frequency sweep is
applied to the transmit plates corresponding to the mass range of
interest. As each ion of a particular mass moves into resonance a
superposition of image currents is generated in the detect circuit. The
signal is amplified, digitized by an analog to digital converter and
stored in a computer. The rapid sweep/detect is repeated many times to
improve the signal-to-noise ratio by signal averaging. The computer
then performs a Fourier-transform on the stored data. This mathematical
procedure can analyze any complex time domain signal to present
graphically a plot of amplitude vs. frequency (mass), thereby producing

22
a mass spectrum. The high mass range is determined primarily by the
magnitude of the magnetic field, with increasing resolution toward lower
masses. A 3 tesla field yields good mass resolution up to approximately
3000 amu. Thus, the FTICR technique has the high resolution at large
m/z values required to study many higher molecular weight metal
complexes. The lower mass limit is governed by the maximum rate of
signal digitization. With a 5.2 MHz digitizer and a 3 tesla magnet,
this limits the detectable masses to >17 amu. A lower magnetic field
allows the detection of important lower mass ions such as OH' with an
accompanying decrease in high mass resolution.
Manipulations of ions in the trap
Between the ionization and detection events any one ionic mass can
be kinetically excited by application of a single frequency pulse via
the transmit plates. A range of masses can be excited by a frequency
sweep. Selected ions can be ejected from the cell completely if they
absorb sufficient energy to spiral out to orbits of such large radius
that they strike the cell plates (ion ejection). If a low amplitude
pulse or sweep is applied, the kinetic energy of the ions can be
increased without ejecting them from the cell.81 This technique can be
used to explore endothermic reaction channels by increasing the energy
of reactants, and this translational excitation is one way by which
structural and thermodynamic information can be obtained. An important
factor contributing to the great versatility of FTICR is that tailored
pulse sequences can be applied in almost any combination.

CHAPTER 2
EXPERIMENTAL PROCEDURES AND RESULTS
Preparation of Trisfhexafluoroacetvlacetonate) Complexes
Scandium and gallium tristhexafluoroacetvlacetonate). To an
aqueous solution containing approximately 1 gram of scandium or gallium
chloride, an excess of ammonia solution was added, which precipitated
Sc(OH)j or Ga(OH)j respectively. The precipitate was filtered, washed
and dried and then refluxed for one hour with a 3-fold molar excess of
hexafluoroacetylacetone (20% in light petroleum ether). When cool, the
reaction mixture was filtered, and the filtrate evaporated to yield
colorless crystals (Sc(hfac)3) or pale orange crystals (Ga(hfac)3). The
crystals were sublimed at 10'3 torr and 40-50°C to effect further
purification.
Titanium and vanadium tris(hexafluoroacetvlacetonate). Both these
complexes are air sensitive and preparation was achieved by using
standard techniques involving Schlenk tubes and a Schlenk argon/vacuum
manifold. A 3-fold molar excess of hexafluoroacetylacetone (20% in
light petroleum ether) was added to approximately 1 gram of VC13 or
TiClj in a Schlenk tube against a flow of argon. The mixture was
refluxed for three hours under a blanket of argon and then allowed to
cool. The solvent containing the dissolved product was decanted from
any unreacted solids into a second Schlenk tube, which had been purged
with argon, prior to the transference by using a cannula with filter
attachment. The solvent was removed by vacuum to yield chocolate
colored crystals (V(hfac)3) or deep blue crystals (Ti(hfac)3). The
products were purified by vacuum sublimation as above.
23

24
Chromium tris(hexafluoroacetvlacetonate). This compound is
available commercially from Strem Chemicals Ltd, and was used as
received.
Manganese trisfhexafluoroacetvlacetonate). The most convenient
and simple method of preparation for this complex was found to be that
reported by Evans and co-workers.55 Approximately 1 gram of Mn203 was
added to a Schlenk tube, followed by a 3-fold molar excess of
hexafluoroacetylacetone (20% in light petroleum ether). The mixture was
refluxed for 48 hours under an argon atmosphere and then allowed to
cool. The resulting black solution was filtered and concentrated to
yield dark green crystals, which were purified by vacuum sublimation.
Only moderate yields of Mn(hfac)3 are obtained by this method, but since
it is simple and convenient, and only milligram amounts were required
for the gas-phase studies reported in this dissertation, the procedure
was adequate.
Cobalt trisfhexafluoroacetvlacetonate). The most convenient
method for the preparation of Co(hfac)3 was also found to be that
reported by Evans.56 To approximately 1 gram of cobalt trifluoride
(CoF3) in a Schlenk tube was added 1 gram of anhydrous sodium fluoride,
which in this reaction acts as a hydrogen fluoride scavenger. A 6-fold
molar excess (to the amount of CoF3) of cooled hexafluoroacetylacetone
was added slowly to the powder mixture and then the reaction mixture was
refluxed for one hour. Note that no solvent is added to the reaction
mixture. During the reflux period the solution turned deep green.
Approximately 20 cm3 of light petroleum ether was then added to the
reaction mixture, which was stirred and then filtered. The solution was
concentrated to yield dark green crystals of Co(hfac)3, which were
purified by vacuum sublimation.

25
Preparation of Tris(acetvlacetonate) Complexes
All the M(acac)3 complexes were purchased (Strem Chemicals Ltd.)
except for Ti(acac)3. The compounds were purified before use by vacuum
sublimation. The Ti(acac)3 complex, like Ti(hfac)3 is air sensitive,
and it is necessary to exclude atmospheric oxygen from the reaction
mixture during preparation by using Schlenk apparatus as was done for
V(hfac)3 and Ti(hfac)3. The complex was prepared by slowly adding a
mixture of 2 grams of acetylacetone and 2 grams of triethylamine to a
solution of approximately 1 gram of TiClj stirring in 25 cm3 of ethanol,
under an argon atmosphere. The reaction mixture becomes hot during the
addition and refluxing is not necessary. Formation of the complex is
accompanied by a dark blue coloration in the solution. After stirring
for 1 hour the solution containing the dissolved product was transferred
to a second Schlenk tube that had been purged with argon. The solvent
was removed by vacuum to yield dark blue crystals of Ti(acac)3>
Purification was effected by repeated recrystallization from degassed
ethanol/water mixtures. The product was further purified by vacuum
sublimation before use.
Preparation of Ruthenium Tris(B-diketonates)
The ruthenium B-diketonate complexes investigated in the present
work are Ru(hfac)3, Ru(tfac)3 and Ru(acac)j. The complex Ru(hfac)3 is
available from Strem Chemicals Ltd and was used as received. The other
two complexes were prepared by using the "ruthenium blue" method
reported by Endo and co-workers.82 Approximately 2 grams of hydrated
ruthenium chloride was placed in a 500 cm'3 three necked round bottom
flask purged with argon. A degassed mixture of 100 cm'3 of de-ionized
water and 150 cm'3 of ethanol was added. The mixture was refluxed on a
steam bath for approximately 2 hours under a blanket of argon. During

26
this time the initial orange color of the solution became almost black.
A 9-fold molar excess of ligand (trifluoroacetylacetone or
acetylacetone) was added to the reaction mixture which was then allowed
to continue refluxing for an additional hour, during which time the
solution became red. Next, 12 grams of potassium hydrogen carbonate
dissolved in 50 cm'3 of de-ionized water was added to the flask dropwise
over a period of 10 hours while the reaction mixture was continued to be
refluxed. The flask was cooled and the solvent was evaporated by using
a rotary evaporator. Benzene was added to the flask to dissolve the red
residue, which was then washed with three 100 cm'3 portions of 1 M
sodium hydroxide solution. The washed benzene solution was dried by
standing over anhydrous sodium sulfate. Finally, the product was
purified by loading onto a 1/2" chromatography column packed with 180
mesh alumina. The column was eluted with benzene and the resulting
solution concentrated to yield orange crystals (Ru(acac)3) or red/orange
crystals (Ru(tfac)j). No further purification of these compounds was
found to be necessary.
Organic Compounds
The organic compounds employed in the present study were purchased
from commercial sources and used without further purification. No
extraneous or fragment ions were detected in their negative ion mass
spectra.
Electron Attachment Studies
The electron transfer equilibrium method. In this section the
general method for the determination of free energies of electron
attachment of volatile polyatomic molecules by means of the charge-
transfer equilibrium method is discussed. Basically, the time

27
dependence of the populations of parent negative ions formed from a
mixture of known partial pressures of two reactants are monitored as
they charge transfer with the neutrals. For the reactions indicated in
eq 2-1, the free energy involved for electron capture by species B can
be bracketed within the lower limit of the known value for A and the
upper limit of the known value for C.
A* + B -* A + B"
B* + C -» B + C 2-1
When the free energy change is small (<3 kcal with FTICR) as in the case
of eq 2-2, the equilibrium populations of the ions can be measured.
A' + B =xn a + b" 2-2
The neutral reactants are in large excess and their partial pressures do
not vary during the reaction. The equilibrium constant for the reaction
in equation 2-2 can be obtained from the ratio of the equilibrium
population of the two ions, and the ratio of the partial pressures of
the reactant gasses. Measurement of gas pressures on the mass
spectrometer is achieved by using an ion gauge. The ion gauge was
calibrated for each reactant by using an external MKS baratron
capacitance manometer in the pressure range of ~ 10"5 torr. Special
pressure calibration procedures developed for the FTICR systems were
used that ensure uniform reactant gas pressure throughout the system by
adjusting the relative pumping rates of the two diffusion pumps
connected to the high vacuum chamber.83 The equilibrium constant Kpxn
leads to the difference in adiabatic free energy of electron attachment
for the two reactants (AG_°), by substituting K _ into eq 2-3.
AGrXn° = -RT ln(Krxn)
2-3

28
The charge-transfer equilibrium method has been used in ICR
experiments16'19 and PHPMS experiments10'15 to provide electron attachment
energies for a large number of organic compounds. For many of the
organic compounds studied, the corresponding entropy change (ASrxn°) and
enthalpy change (AHrxn°) have been obtained by following the temperature
dependence of the equilibrium.11 <12<1^»15 The results have produced
ladders of multiple overlapping values of AGrxn°, AHrxn° and ASrxn° for
pairs of organic reactants such as substituted benzophenones,19
nitrobenzenes,10,11,13,17-19 quiñones14,19 and dicarbonyls.15 The absolute
values for electron capture by each compound, (defined by AGa°, AHg° and
ASa° for the reaction A + e- = A') are obtained by including an external
standard in the ladders for which AH 0 and As ° are well established.
a a
For example the EA of SC>2 has been accurately determined to be 1.097 ±
0.036 eV84 and 1.107 ± 0.0008 eV85 in two independent investigations of
the photoelectron spectroscopy of S02‘, and S02 is the reference
compound chosen in the EA investigations of Kebarle. The value for ASg°
was evaluated by the methods of statistical mechanics from structural
and spectroscopic data.11
Electron attachment and electron transfer equilibrium studies
using the Nicolet FT/MS 1000. Gas-phase charge-transfer reactions of
the type outlined in eq 2-1 and in eq 2-2 were studied in the present
work by using a Nicolet FT/MS 1000 Fourier transform ion cyclotron
resonance mass spectrometer (FTICR). A diagram of the instrument used
is given in Figure 2-1. The technique used in the present work was
similar to that reported previously in ion cyclotron resonance mass
spectrometry (ICR) and pulsed high pressure mass spectrometry (PHPMS)
investigations. The temperature of the reaction cell was measured under
normal operating conditions to be 350 K. For the electron-transfer
reactions studied in which a charge-transfer equilibrium was observed
between an organic reference compound and a metal complex, the value of
AGa° for the complex was obtained from the value of AGrxn° given by the

29
Diffusion Pump
Inlet Diffusion Pump
Figure 2-1. Schematic diagram of the Nicolet FT/MS 1000.

30
measured equilibrium constant, and a value of AGa° for the organic
compound at the reaction temperature of 350 K (obtained for each organic
compound from the tabulated values of AHg° and Asa°). Most of the
organic compounds and the M(hfac)3 complexes were sufficiently volatile
to admit into the mass spectrometer through leak valves without heating.
Less volatile organics and the M(acac)3 complexes were sublimed off the
tip of a solids probe placed well away from the ion trap, which was at a
temperature of " 350 K. Negative ions were produced from neutrals in
the FTICR trap by capture of low energy electrons (< IV). Electron
capture by the metal complexes was, in most cases, accompanied by
varying amounts of fragmentation. Parent ions were selected from these
fragments by ion ejection techniques.
To approach collisional thermalization of ions prior to the
ion/molecule reaction, FTICR relies on a set thermalization period
between ionization and detection of product ions. Typical reaction
pressures in this study were in the 10'6 torr range, but a bath gas such
as argon or cyclohexane can be added to reactant mixtures if lower
reactant pressures are used. For both bracketing and equilibrium
experiments a thermalization period of 1 s was used. Assuming a second
order collision rate constant of 10'9 cm3 molecule’1 sec’1, at a total
pressure of 10'6 torr, each ion collides an average of about 30 times
with neutral reactant molecules before charge-transfer reactions were
followed. When a charge-transfer equilibrium was observed, the ion
populations were determined by measuring the relative abundance of the
two parent ions over suitable time intervals until they reached a
constant value. The equilibration could be followed for long reaction
times (to " 20 s) ensuring complete thermalization. At the reactant
pressures in this study equilibrium was usually established within "3
seconds, and ion loss from the cell was negligible during this time.
Ejection of each parent ion prior to equilibrium was to show that
equilibrium constants obtained do not depend on direction of approach to

31
equilibrium. The electron attachment energies for all the compounds
studied are presented in Table 2-1. The results are also presented in
Figure 2-2 to illustrate the organic reference compounds that were used
in the present work.
Table 2-1. Free Energies of Electron Attachment (kcal mol'1) at 350 K
for Mlacaclj, Mftfac^ and M(hfac), Complexes.
Sc(hfac)3 -64 ± 3C
Sc(acac)3 > 0
Ti(hfac)3 -69 ± 3C
Ti(acac)3 < 0
V(hfac)3 -73 ± 2b
V(acac)3 -24.9
Cr(hfac)3 -67 ± 3C
Cr(acac)3 -20 ±
Mn(hfac)3 (-109)a
Mn(acac)3 -59 ±
Fe(hfac)3 (-93)a
Fe(acac)3 -43.0
Co(hfac)3 (-97)a
Co(acac)3 -47 ±
Ga(hfac)3 -60.4 ± 0.5b
Ga(acac)3 > 0
Ru(hfac)3 (-89)a
Ru(acac)3 -38.7
Ru(tfac)3 -64.0b ± 0.5b
Estimated values obtained by adding 50 kcal mol"1 to corresponding
value for M(acac)3 complex (see text).
'Value obtained from measured equilibrium constant.
Reference compounds given in Figure 2-1
cValue obtained by bracketing (see eq 2-1).

32
CN
:c=c; -
CN CN
Chlorine atom 83.4
CN
j Mn(hfac)3 (109)
| Co(hfac)3 (97)
h Fe(hfac)3 (93)
j—Ru(hfac)3 (89)
73
• V(hfac)3 73-
Cl Cl
Oi/Vo-^ ,— Ru(tfac]ij 64.0 t
J. C. - - 1
°y°
F F
Cl Cl
•62.8
61.1
-Ti(hfac)3 69
-Cr(hfac)3 67
• Scfhfac^ 64
Cl
O^0=°-56.O-
CN Cl
\_Ga(hfac)3 60.1
Mn(acac),j 59
Co(acac)3 47
Fe(acac)3 43.0
Ru(acac)3 38.7
V(acac)3 24.9
Crfacac^ 20
/
Figure 2-2. Free energies of electron attachment (kcal mol'1) to
M(acac)j and M(hfac)j complexes at ~350 K and reference compounds used.
A continuous line linking an organic compound and a metal complex
indicates the value for the complex was obtained from a measured
eguilibrium constant. Arrows indicate the compounds of greater and
lower AGa° values used to bracket the value for the metal complex (eq
2-1). Values for M(hfac), with M = Mn, Co, and Fe are estimates (see
text).

33
Electron attachment energy of acac radical. The electron
attachment energy of acetylacetonate radical was determined by the
bracketing method, in which the occurrence or non-occurrence of charge
transfer reactions involving acac' ions with organic reference compounds
were observed (eq 2-1). The acac' ions were generated by heating
Co(acac)3 off the tip of a solids probe to produce a low partial
pressure (~10'7 torr) of Co(acac)3 in the FTICR main chamber.
Acetylacetonate anions were produced following electron impact
ionization of the gas. By following the time dependence of the
population of acac" ions in the presence of approximately 10‘6 torr of
each of a series of organic reference compounds, it was determined that
acac" charge-transferred to 2,6-dichlorobenzoquinone, but not
tetrafluorobenzoquinone, which sets the limits of the electron
attachment energy at 59 ± 3 kcal mol"1 (see Figure 2-2).
Consistency of Electron Attachment Energy Determinations. Although
the lower operating pressures of ICR and FTICR, compared to PHPMS,
enable low volatility compounds to be studied,86 this also introduces a
greater uncertainty in the measurement of reactant pressures. To check
the consistency of the results obtained in the present work with those
of previous determinations, AGrxn° for the reaction A = 1,4-
dicyanobenzene; B = 3-fluoronitrobenzene was measured. For this
reaction at 423 K Kebarle12 has found AG.® = -3.2 kcal mol*1 and AS 0 =
rxn rxn
2.5 cal mol"1 K"1 giving a value of AHrxn° of -2.1 kcal mol"1. In the
FTICR at 350 K we obtained AGrxn° = -2.8 kcal mol"1 which together with
the previously determined entropy change gives AHrxn° = -1.9 kcal mol"1.
The discrepancy of 0.2 kcal mol'1 probably arises from the uncertain
temperature of the neutral gas and error in measuring equilibrium
constants that are close to the limit of detection (0.01 our instrument. The value of AGrxn° for this reaction therefore
represents a value close to the upper limit of the range of values that
may be confidently measured. The discrepancy can be considered an

34
estimate of the expected error for free energies determined for
equilibrium reactions, and conservative uncertainties of 0.5 kcal mol"1
are assigned to values of AGg° determined by equilibrium to account for
experimental uncertainties, including temperature, pressure and
uncertainties in the assigned thermodynamic quantities for most of the
reference compounds.
Electron attachment to trisfhexafluoroacetvlacetonate) complexes.
The M(hfac)3 complexes studied in this investigation were those of the
first row transition metals from Sc-Co, Ga and Ru. These complexes are
particularly volatile and are easily admitted into the FTICR through
leak valves on the inlet system. It has been shown previously70,71 that
for a series of first row transition metal M(hfac)3 complexes that
fragmentation following electron capture increases from left-to-right in
the row. The same general trend was observed in the FTICR in this work.
The major pathway to fragmentation was loss of a ligand ion, and this
ion predominated in the mass spectra of the Fe and Co complexes
immediately after electron capture. A few hundred milliseconds after
the ionization, the parent ion was formed by charge transfer to the
neutral complex from the fragment ions. After a suitable period of
time, any remaining fragment ions were ejected from the cell.
By observing charge-transfer reactions involving M(hfac)3
complexes and organic reference compounds, it was found that few had
-AGg° values as high as that of the complexes. The Fe, Co and Mn
complexes had values greater than any of the organic compounds so far
reported. Although AGg° values could not be experimentally measured for
Fe(hfac)3, Co(hfac)3 and Mn(hfac)3 estimates were obtained by noting
that the order of the AGg° values runs parallel to the series of
M(acac)3 complexes. For the series of M(hfac)3 complexes, the order of
increasing values of -AGa° at 350 K was found by bracketing the
complexes against each other. Roughly equal pressures of various
combinations of two M(hfac)3 complexes were admitted into the FTICR, and

35
it was observed which of the two parent negative ions predominated after
a charge transfer period, the relative order for the series of
complexes was determined. The difference in AGa° values between
V(acac)3 and V(hfac)3 was determined to be "50 kcal mol’1 from the
results of two separate equilibrium reactions. Assuming a constant
difference of 50 kcal mol'1 between the M(acac)3 and M(hfac)3 complexes
of the other metals in the series, estimates could be made for the
M(hfac)3 complexes (M = Ru, Fe, Co, Mn) since those for the M(acac)3
complexes of the same metals were measurable. Values of AG ° obtained
in this way have been put in parentheses in Table 2-1.
The substance with the highest accurately known electron affinity
is the chlorine atom, and Cl'(g) ion was included in the study of charge
transfer reactions with the metal complexes. Electron capture by a
background pressure of Fe(hfac)3 with a small partial pressure of benzyl
chloride produced Cl"(g) in addition to the ions formed from the metal
complex. It was found that when all ions except chloride were ejected
from the cell and its subsequent reaction with Fe(hfac)3 was followed,
chloride ion regenerated Fe(hfac)3' by charge transfer, indicating that
the electron attachment energy of Fe(hfac)3 > 83.4 kcal mol’1,87 in
accord with the value estimated above.
Charge transfer occurred from tetrachlorobenzoquinone (C14BQ) to
Cr(hfac)3, but an equilibrium reaction was not observed in the reaction
with Sc(hfac)3 as the reaction was hampered by rapid formation of adduct
ions [Sc(hfac)3.Cl4BQ]', and [Sc(hfac)3]2'.
Electron attachment to tris(acetvlacetonate) complexes. M(acac)3
complexes were studied for the series of metals Sc-Co, Ga and Ru. It
has been previously noted that the cross-section for electron capture by
first row transition metal M(acac)3 complexes is much lower than for the
corresponding M(hfac)3 analogs.88 Indeed, Cr(hfac)3 was shown to have an
electron capture cross-section some 5000 times greater than CriacacJj.88
This was attributed to the six electron withdrawing CF3 ring

36
substituents in the former. The same general effect was observed in
this report for the complexes of the metals Cr to Co. The only ion
produced from ionization of the neutral gas with the electron beam was
ligand anion, but unlike the M(hfac)3 complexes, the ligand ion did not
charge transfer to the neutral complex to form the parent ion. Parent
negative ions of these complexes could only be obtained in reasonable
yields following chemical ionization by an organic compound of lower
electron attachment energy. In performing experiments with these
compounds, therefore, it was necessary to eject relatively large amounts
of ligand anion from the cell. The Ti and V complexes produced no
detectable fragment ions and had large cross sections, in accord with
the trends in stability of the ions noted above.
The difference in the electron withdrawing effect between CF3 and
CH-j in the two series of complexes was also observed to markedly reduce
the values of AGg° for the M(acac)3 series relative to the M(hfac)3
series, and the values of AGg° fall well within the range of those of
the organic compounds in the reported electron transfer free energy
ladder, which extends from approximately 10-75 kcal mol'1. This enabled
the bracketing and equilibrium reactions in eq 2-1 and eq 2-2 to be
followed for the entire series of M(acac)3 complexes. The Cr(acac)3
ion, although initially produced in the FTICR cell, was unstable and
underwent rapid loss of ligand ion at a rate that increased with the
total pressure of the system, indicating a collisionally induced
dissociation. The instability of the Cr(acac)3‘ has been observed
previously.89 Bracketing this compound through charge-transfer
reactions was therefore hampered by competitive ligand loss, producing a
greater uncertainty in the result. Parent negative ions could not be
\
made for the Sc and Ga complexes. Assuming a parallel trend between the
M(hfac)3 series and M(acac)3 series, then the Sc and Ga complexes would
be expected to have AGg values too low for formation of a stable anion,
and, experimentally no parent ions were observed.

37
A value of AGa° for the Ti(acac)3 complex could not be obtained.
In contrast to all the other complexes studied, Ti(acac)3 or its anion
did not undergo detectable electron exchange in the time scale
obtainable with the FTICR, even with relatively high pressures of
neutral gas. Exothermic charge transfer reactions involving Ti(acac)3
with various organic reactants were too slow to follow (k /k ... . <
10'4) over the range of up to 1 eV of driving force. The cause of this
unexpectedly slow gas-phase charge transfer is not known and would not
have been predicted for a d1/d2 redox process.
Charge-transfer equilibria were observed for the V and Fe
complexes, and results for Cr, Mn and Co were obtained by the bracketing
technique outlined in eq 2-1.
Gas-Phase Spectrophotometry of Cr(hfac),
The gas-phase visible spectrum of Cr(hfac)3 was determined in
order to compare the spectrum to that of Cr(hfac)3 in solution (see
chapter 6). The gas-phase spectrum was obtained by using a specially
designed sample cell with 10 cm path length and fitted with heated
quartz windows and separately heated cell body. The body was maintained
at a temperature a few degrees cooler than that of the cell windows to
ensure that crystals of Cr(hfac)3 did not form on the windows and render
them opaque. Crystals of Cr(hfac)3 were added to the cell, which was
then evacuated and positioned in the cell compartment of an IBM
UV/visible 9430 spectrophotometer. The cell was gradually heated to
about 80° C to produce a practical concentration of vapor.

CHAPTER 3
TERMINOLOGY AND CONVENTIONS USED IN GAS-PHASE ION THERMOCHEMISTRY
Introduction
Values for the energy required to remove an electron from an
isolated atom, molecule or ion are often obtained by using spectroscopic
methods that yield the minimum energy required for this process. This
energy is the adiabatic ionization potential (alP) for neutral or
positively charged species and the electron affinity (EA) for anionic
species. Mass spectrometric methods and other techniques have also been
used to estimate values for electron attachment energies and ionization
energies at T = 0 K as well for T > 0 K. In combination with other
thermochemical data, alP and EA values provide fundamental information
concerning the thermochemistry of ionic processes such as charge-
transfer reactions and ion solvation. For example, extensive
compilations of enthalpies of formation of ions at 298 K (AHf°) derived
from spectroscopic and mass spectrometric data are available.90
Tabulated values for AHf° of ions depend on the convention used to treat
the gas-phase electron.90®'91 Therefore, a convention must be used
consistently to avoid errors in derived data. One convention, the
thermal electron convention (TEC), is widely used by thermodynamicists
and treats the electron gas as a classical ideal gas. The stationary
electron convention (SEC) ("ion convention") is more commonly used by
mass spectrometrists and treats the electron as a subatomic particle.
Presented here are definitions of some important terms frequently
encountered in discussions of the energies of electron attachment or
detachment processes for gas-phase ions and neutral molecules. Also
included is a discussion of the two thermochemical conventions in common
38

39
use. The stationary electron convention is adopted throughout the
present work, and the free energies of electron attachment to the metal
complexes obtained in the present work conform to this convention.
Since a discussion of the stationary electron convention applied to free
energies of electron attachment and ionization processes has apparently
not appeared in the literature, a discussion is give here.
Electron Affinities and Adiabatic Ionization Potentials
The electron detachment process for a monoatomic or polyatomic
species Mn is shown in eq 3-1 (where n is the charge and can be zero,
positive or negative).
Mn(g) = M0*1 (g) + e' 3-1
The enthalpy change for electron detachment (AH°(Mn -» Mn+1)) can be
expressed as the sum of the enthalpy change at 0 K and the difference in
heat contents of the products and reactants at temperature T, given by
the difference in the integrated heat capacities over the range 0 K to T
(eq 3-2).
T T T
Ah °(Mn-Mn*1) - AE0_0+JcpiM"*1) dT + Jcp(e-) dT-|cp(Mn) dT 3_2
0 0 0
The term AEq.q is the energy required to form Mn+1 in its ground
electronic, rotational, and vibrational states from Mn in its ground
state. When Mn is a negative ion, AE0_0 defines the electron affinity
(EA) of Mn+1. When Mn is a neutral or positively charged species, the
energy is defined as the adiabatic ionization potential (alP). The
vertical energy for the process in eq 3-1, usually obtained from the
results of photoelectron spectroscopy, involves the formation of Mn+1
with the same geometry as that for Mn.

40
If the geometries of Mn and M^1 differ, Mn+1 will be formed in an
excited state and the energy required for the vertical processes may
be greater than for the adiabatic process.
Stationary and Thermal Electron Conventions
Usually, though not always, Mn and M0*1 in eq 3-1 are chemically
similar and the difference in their integrated heat capacities can be
neglected with respect to that of the electron. The thermal electron
convention, however treats the electron gas in eq 3-1 as an ideal gas,
which has an integrated heat capacity at constant pressure of 5RT/2,
while under the stationary electron convention the heat capacity of the
electron is set to zero. The relationship between the enthalpies of
electron detachment between the two conventions is given in eq 3-4.
AH°(TEC) - AH(SEC) = 5RT/2 3-3
The free energy change for the process in eq 3-1 at a temperature T can
be written in terms of the associated enthalpy and entropy changes
(eq 3-4).
AG°(Mn -» Mn+1) = AH°(Mn -» Mn+1) - TAS°(Mn -» Mn+1) 3-4
The value of n in eq 3-4 for free energy values derived from
experimental charge-transfer equilibrium studies10'19,92 is limited to 0
and -1. The total entropy change for the electron detachment process
(AS°(Mn -» Mn+1)) is equal to Sppoducts° - Speactants° (= S°(e') + S°(Mn+1) -
S°(Mn) ), and can be written as the sum of the translational, rotational,
vibrational and electronic entropy changes eq 3-5.
AS°(Mn -» M^1) = AStrans° + ASrot° + ASvjb° + ASelec° 3-5

41
Since the masses of M"*1 and Mn only differ by the mass of an electron,
Strans° *or Mn+1 and virtually identical and these terms in eq
3-5 will essentially cancel. In eq 3-1 Astrans° is therefore negligibly
different from Strans°(e )• The translational entropy of an ideal gas of
particles of mass m can be predicted from statistical mechanics by the
Sackur-Tetrode equation93 (eq 3-6) where V is the volume of the gas, k
is the Boltzmann constant, L is Avagadro’s constant h, is Planck’s
constant and T is the temperature.*
q °
^trans
3-6
The term ASetec° is given by eq 3-7, where Qeiec is the electronic
partition function.
ASelec° = R ln (Qelec(Products)/Qelec > 3-7
The electron has an electronic degeneracy of 2, and eq 3-7 can therefore
be rewritten as eq 3-8.
ASelec° = R ln /Qelec> + R ln2
3-8
The free energy for electron detachment given in eq 3-2 can now be
given according to the two conventions. The thermal electron convention
includes the terms for the electron gas, and Ag° for electron detachment
is given by eq 3-9.
*Although the Sackur-Tetrode equation gives good agreement between
experiment and theory for the translational entropy of an atomic or .
molecular gas, the equation predicts negative entropies for T < 89 K for
a particle with the mass of an electron. The assignment of the electron
gas as an ideal gas is a completely arbitrary convention since it is
well known that a mole of gaseous electrons is more realistically
described by Fermi-Dirac statistics rather than Boltzmann statistics
under almost all experimental conditions.

42
T T
AG ° (TEC) - AE0_0 + I Cp(Mn*1) dT- JcpiM") dT + -|rT
0 0
- T(ASrot + ASvjb + R ln(Qelec(Mn+1)/Qelec(Mn)) + Strans(e-) + R In 2) 3-9
The stationary electron convention neglects all terms for the electron
gas and Ag° of electron detachment is given by eq 3-10.
T T
AG ° (SEC) - AE0_0 + JCp (Mn+1) dT - f Cp (M n) dT
0 0
- T( Asrot + ASvjb + R ln(Qelec(Mn+1)/Qelec(Mn)) ) 3-10
The temperature at which the two conventions give the same value for
AG°(Mn -» Mn+1) for any species M can be found by subtracting the right
side of eq 3-10 from the right side of eq 3-9 and setting the difference
equal to zero (eq 3-11).
5RT/2 - T(Strans°(e’) + R In 2) =0 3-11
Collecting the constant terms from the Sackur-Tetrode equation gives the
difference between AG° values for each convention at any temperature,
(eq 3-12).
[AG°(TEC) - AG°(SEC)]/J mol'1 = T (118.35 - 8.3145 ln(T)5/2) 3-12
At 0 K, AG0 of electron detachment is equal to the alP or EA values, and
there is no difference between the two conventions. However eq 3-11 is
also equal to zero at 296.96 K, and the two conventions give identical
values for AG at this temperature.
The two conventions applied to simple systems are shown
graphically in Figures 3-1 and 3-2. For M = hydrogen atom, Ag°(H -> H+)
values given by eqs 3-9 and 3-10 are plotted in Figure 3-1 (a). For

43
this system the heat capacity terms for H atom and H+ ion cancel, and
ASrot° and ASvib° are equal to zero. The intersection of the two lines
occurs at 296.96 K where the two conventions give the same value. The
values for each convention at 298 K are within '0.02 kJ mol'1 and so can
be assumed to be approximately equal at this commonly used standard
temperature.
The significance of the result for the hydrogen atom can be seen
in calculations of the absolute thermodynamic potential of the standard
hydrogen electrode,94,95 given by the standard free energy change for eq
3-13.
H+(aq) + e* (g) = 1/2 H2 (g)
3-13
The value of AG° for eq 3-13 can be expressed as the sum of the AG°
values for three elementary steps,94,95 one of which involves the
ionization of a gaseous hydrogen atom, eq 3-14.
H-(g) = H+(g) + e’ (g)
3-14
The value of AG° for this process, and hence the value for the absolute
electrode potential (or "single electrode potential")94,95,9®'9® depends
ultimately on which electron convention is used. The absolute value of
the standard hydrogen electrode is used to obtain the absolute AG° of
electron attachment to molecules in solution. As noted above, by
coincidence there is virtually no difference between the two conventions
at 298 K (absolute E° = 4.44 V) This allows, for example, direct
comparison between data for free energies of electron attachment to gas-
phase molecules, usually obtained under the stationary electron
convention, to the absolute electrode potential of the same system in
solution, usually derived under the thermal electron convention, with no
significant error for T = 298 K due to mixing of conventions.

44
Also shown in Figure 3-1 (b) is a plot of AG0 (I2 -» I2+). Fot this
process appropriate spectroscopic data is available99’101 for I2 and I2+
to allow calculation of the relevant heat capacities, ASrot°, and ASvib°.
The obvious difference between the plots of AG° for the ionization of H
atom and I2 is that the slope for the ion convention values are
opposite. Under the ion convention only the electronic degeneracy of Mn
and Mn+1 is considered and so ASelec° is never equal to zero. Ionization
of H results in a loss of electronic degeneracy (ASelec° = R In 1/2 in
the SEC). For I, a 2H state is formed from a 12„ state, and As^. ° = R
In 3 in the SEC. For most small molecules such as I2 the TAS0 term
arising from a change in electronic degeneracy will produce the largest
difference between the alP of a polyatomic molecule and AG° of
ionization at T > 0 K. The difference in the integrated heat capacities
of I2 and I2+ differ by only 0.09 kJ mol'1 at 298 K and the combined
values of TASrot° and TASy-b0 only amounts to "0.5 kJ mol’1 at 298 K,
somewhat smaller than the contribution from TAS , °. Further, the
elec
enthalpy change arising from the change in the integrated heat
capacities will always have the same sign as the entropy change and
these terms will cancel in the final expression. The predominance of
the ASe^ec° term produces the almost linear change in free energy (SEC)
with temperature as shown in Figure 3-1.
Exactly analogous plots of Ag° of electron attachment to an ion or
neutral molecule under the two electron conventions can be obtained by
plotting the negative of the electron detachment values given in eq 3-9
and 3-10. The AG0 of electron capture for S02 has been calculated by
Chowdhury and co-workers11 at 423 K from the electron affinity8^ of S02
combined with spectroscopic and theoretical data for the geometries and
vibrational frequencies S02 and S02'. The calculation was repeated here
both electron conventions over a range of temperatures, using the same
data (Figure 3-2).

45
The electronic degeneracy change is dominant in the stationary electron
convention, and the dependence of AG°(SEC) on T deviates only slightly
from linearity over the temperature range shown.

Free Energy of lonization/eV
46
Figure 3-1. Plot of the free energies of ionization calculated by using
the thermal electron convention (TEC) and the stationary electron
convention, (a) Atomic hydrogen; (b) Diatomic iodine.

AG of Electron Attachment/eV
47
Termperature/K
Figure 3-2. Plot of the free energy of electron attachment to S02
calculated by using the thermal electron convention (TEC) and the
stationary electron convention (SEC).

CHAPTER 4
INTRAMOLECULAR ENTROPY CHANGES FOR REDOX
COUPLES INVOLVING COMPLEX METAL IONS
Introduction
Entropy changes that occur for electron attachment to gas-phase
polyatomic molecules (Asa°) have been obtained by determining the
temperature dependence of equilibrium constants for gas-phase charge-
transfer reactions (KeC) in eq 2-1) by the procedures described in
chapter 2. The entropy change is obtained from a Van't Hoff plot of the
data. The types of compounds studied to date have been predominantly
organic compounds with delocalized n systems, often containing electron
withdrawing substituents. For these compounds, values of ASa° are small
and typically fall in the range of ± 4 cal mol'1 K'1. An important
consequence of this result is that AGa° and AHa° values are approximately
equal and constant over a wide range of temperatures. In fact, AGg°
values for the organic compounds that have been studied, which are
usually measured at temperatures above 300 K, are typically within 2
kcal mol'1 of their values at 0 K; that is, their electron affinities.
The electron attachment energy data may therefore be combined with other
compiled enthalpy or free energy data at 298 K or at other temperatures
without introducing serious errors.
It is useful to obtain data for the temperature dependence of gas-
phase charge-transfer reactions involving organometallic and
coordination compounds since a more complete understanding of the
thermodynamics of electron attachment at metal centers can be gained.
Additionally, gas-phase AHg° data for organometallic and coordination
compounds, which is obtained from such studies, can be combined with a
48

49
variety of calorimetric thermochemical data for metal-containing
compounds in energy cycles that provide thermodynamic data that are
difficult to obtain by more conventional methods. Examples of the
application of gas-phase electron attachment energies in energy cycles
are given in chapter 5.
Organometallic and coordination compounds are chemically dissimilar
to the types of organic compounds that have been studied and it can not
be assumed that ASg° values for these types of compounds will also be
small in all cases. Temperature dependent gas-phase charge-transfer
equilibrium studies involving metal containing compounds are rare. For
n4-butadiene iron tricarbonyl, ASa° has been quoted to be 10 + 3 cal
mol'1 K'1,* considerably higher than the typical values found for the
organic compounds that have been studied. In principle similar data
could be obtained from FTICR studies if some means were available to
control the temperature of the reaction cell and main chamber (Figure
2-1). Unfortunately, in the determination of AGa° for the metal
complexes reported here, such a facility was not available and entropy
changes could not be measured.
Despite the general lack of experimental data for gas-phase electron
attachment entropies for coordination complexes, data are available from
other sources. Estimates for certain couples can be obtained from
statistical thermodynamics calculations when there are sufficient
structural and vibrational data.
For example, Lowenschuss and Marcus102 have used statistical
mechanics calculations to calculate standard gas-phase entropies for a
large number of polyatomic ions, including the members of the redox
Private communication with G. W. Dillow

50
couples IrCl63'^2' and Fe (CN)6^"/3‘.
Another source of data for entropy changes involving the reduction
of metal complexes is from studies of the temperature dependence of
electrochemical E1/2 values by using cyclic voltammetry. Entropy
changes for half-cell redox couples involving several octahedral and
tris chelate complexes have been obtained in the laboratories of Weaver
and co-workers,103*103. These studies have been primarily concerned with
the relationship between the rate of electron transfer processes between
metal centers in solution and the enthalpic and entropic contributions
to the overall driving force of the reaction.106 Entropy changes for
redox half-cells (Asrc°) obtained by the cyclic voltammetry method are
consistent with the stationary electron convention for dealing with
entropies of electron attachment to gas-phase molecules, since the
electron in the reduction originates from the electrode and cannot be
considered as an "electron gas”.
Comparison of data for gas-phase and solution-phase entropy changes
for a particular redox couple leads to the separation of the observed
entropy change in solution into an intramolecular contribution, plus a
contribution from solvent polarization. Such comparisons can not only
provide considerable insight into the magnitudes of entropy changes for
electron attachment to gas-phase coordination complexes, but also lead
to a greater understanding of the role of the solvent in determining the
overall change in entropy for a particular redox couple.
Presented here are the results of statistical mechanics calculations
of the entropy changes involved for electron attachment to some gas-
phase octahedral complexes. The examples given are for complexes that
form stable redox couples in solution. Calculations are repeated for
the ions that form the couples IrCl62*^3’ and Fe(CN)63"^*, which were
originally reported by Lowenschuss and Marcus, but the results are
discussed in the context of the factors that govern the magnitude of
intramolecular entropy changes in redox couples. Calculations are also

51
performed for the ions in the couples Ru (NHj)63+/^+, Co(NHj)^3+/^+ and
WC16°^’. Comparisons are made, where possible, between the theoretical
data obtained here and the experimental data reported in the literature.
The insight gained is used to provide estimates for the gas-phase
entropy changes that occur for electron attachment to M(acac)j and
M(hfac)3 complexes.
Statistical Mechanics Applied to the Determination of
Gas-Phase Intramolecular Entropy Changes for
Redox Couples Involving Complex Metal Ions.
Electron attachment to coordinated transition metal centers is often
into a metal based molecular orbital. The changes in metal-ligand
bonding that result can shift the frequencies of metal-ligand skeletal
vibrations, change the moment of inertia of the molecule by shifting
metal-ligand bond lengths and change ground state electronic
degeneracies. These internal rearrangements redistribute the internal
energy of the molecule or ion and lead to an intramolecular entropy
change (ASj(gas)0). The total change in entropy in the absence of
solvent can be expressed as the sum of the translational, rotational,
vibrational and electronic entropy contributions (eq 4-1).
ASj(gas)0 = ASj(trans)0 + ASjirot)0 + ASj(vib)0 + AS^elec)0 4-1
The contributions ASj(trans)0, AS-(vib)0, etc., for ideal gases can be
evaluated by using the methods of statistical thermodynamics.
Thermodynamic functions can be readily calculated from the appropriate
partition function ( available energy states that are thermally populated, eq 4-2.
<3 - £ 9ie
4-2

52
The value of q in eq 4-2 at a given temperature is dependent on the
degeneracy of the energy states, g-, and the energy separations between
states, AE. The term k is the Boltzmann constant.
The general expression for the rotational, vibrational and
electronic entropies of a system of ideal gaseous particles is given in
eq 4-3.
S
(E-E0)
T
+ R lnq
4-3
The values of As^rot)0, ASj (vib)° and As^elec)0 for gas-phase electron
attachment to a molecule can be found from eq 4-3 by calculating
Sjfrot)0, Sj (vib)° and Suelee)0 for both the oxidized and reduced
species and obtaining the difference between the values for each
species. To evaluate the various contributions to AS1-(gas)0, therefore,
the two terms on the right of eq 4-3 must be evaluated. The term (E-Eg)
is the thermal energy and may also be separated into (E-Eg)trans,
(E-Eg)rot, etc. Thermal energies are calculated from the appropriate
partition function given by eq 4-4.
(E-E0) -RT2 d-j)n^
In statistical thermodynamics calculations of entropies, the
expressions used for As^(rot)0 and ASj(vib)0 are approximations based on
treating the complex as a rigid rotor and the normal modes as harmonic
oscillators. Corrections can be made, but the improvements in the
accuracy of the calculations is small and are not included in the
discussion here. The contributions from ASj(trans)0, ASj(rot)0,
ASj(vib)° and As.(elec)0 to ASj(gas)0 for electron attachment to
octahedral transition metal complexes are discussed below.

53
Changes In Translational Entropy
The translational entropy of a system of ideal particles at a
particular temperature and volume is related to the mass of the
particles. Electron attachment to a molecule has a negligible effect on
the mass and the resulting change in AS-(trans)0 is also negligible. To
evaluate ASj(gas)0, therefore, no consideration need be given to
ASjftrans)0. However, values of gas-phase entropies of single ions are
given below for completeness and a value of (trans)0 is required for
this purpose. The values reported in the present work are given by the
Sackur-Tetrode equation given in eq 4-5.
In eq 4-5, m is the mass of the particle, k is the Boltzmann constant, h
is Plank's constant, V is the volume of the gas and N is Avagadro's
constant.
Changes in Rotational Entropy
The expression for qrot is obtained by substituting the quantum
mechanical expression for rotational energy spacings into eq 4-2. Since
rotational energy spacings are very small compared to kT, the summation
can be replaced by an integral. The result is given in eq 4-6.
<3rot " -^(IABC)3/2(2nkT)3/2
oh* 4-6
Octahedral molecules are classed as spherical tops and the three
principle moments of inertia are the same. The term IABC in eq 4-6 is
the product IAIBIC and is given by IABC = 4mR2 where m is the mass of the
peripheral atoms and R is the distance between the central atom and any
peripheral atom. In eq 4-6, k is the Boltzmann constant, h is Planck's
constant and a is the rotational symmetry number, which is 24 for an

54
octahedral molecule. Substitution of eq 4-6 into eq 4-4 yields the
following expressions for the rotational thermal energy ((E—EQ) rot) Per
mole per degree of freedom.
[E"E0]rot = RT/2
4-7
For all but the lightest ions and molecules the moment of inertia is
large enough that the rotational thermal energy attains its classical
value of RT/2 per degree of freedom. For molecules with a low moment of
inertia the summation in eq 4-2 cannot be accurately replaced by an
integral and must be evaluated either manually, or by using the Euler
Maculaurin summation formula. For this case the thermal energy of the
gas is slightly less than the value in eq 4-7.
For molecules such as octahedral complexes that have 3 degrees of
rotational freedom the thermal energy is 3RT/2. Since the value of
3RT/2 applies to both the oxidized and reduced complex, only ARln q in
eq 4-3 contributes to AS-(rot)0. Substituting eq 4-6 into eq 4-3 gives
an expression for As. (rot)0 for electron attachment to octahedral
molecules, eq 4-8.
4-8
The terms IABC3(red) and IABC3(ox) are the moments of inertia for the
reduced and oxidized metal complex respectively.
In Figure 4-1 a plot is shown of the rotational entropy, given by eq
4-3, for the molecules MF6, MCl6 and MBr6 as a function of increasing
M-X distance at 298 K. It can be seen that all the plots are
approximately linear over the range of typical metal-ligand bond lengths
found in octahedral complexes. Differences in bond lengths observed for
metal complexes that can possess more than one formal oxidation state at
the metal center rarely exceed ± 0.2 Á. From Figure 4-1 the slope of

55
the plots is close to 3 at 2 Á and varies little over the range shown.
This sets an approximate upper limit of ASj(rot)0 of ± 0.6 cal mol'1 K'1
for octahedral metal complexes. The precise value can be calculated
from eq 4-8.
For the complexes considered in this chapter the M-L bond lengths
required for the evaluation of rotational entropies were obtained from
literature sources and the data are given in Table 4-1. All bond length
data are from X-ray crystallography studies except the W-Cl bond length
in WC16, which was obtained in the gas-phase by an electron diffraction
study. Values are not available for the M-L distances in IrCl63' and
WCl6'. The values given for the ions in Table 4-1 are estimated values,
obtained by adding 0.05 Á to the values for IrCl62* and WC16
respectively. For both ions the electron in the lower oxidation state
complex is accommodated in the t2g non-bonding orbital set. Where
structural data are available, this change in M-L bond length is typical
for MX6 ions that are stable in oxidation states of similar electronic
configuration. The error introduced in the value for ASj(rot)0 from
these estimates is small. For the hexacyanoferrate complexes the
rotational entropy was calculated by considering each cyano group as
having an atomic mass of 26.02 amu and situated at the average distance
of the C and N atoms from the metal center (see Table 4-1). For ammine
complexes, rotational entropies were calculated from an effective M-L
bond distance obtained by treating the ammine group as a single atom of
mass 17 amu. The effective M-L distance was calculated from the
appropriate M-N and N-H bond lengths given in Table 4-1.

56
Table 4-1. Metal-Ligand Bond Lengths in Metal Complexes.
Complex
Bond Length/Á
Complex
IrCl62-
(M-L)
2.307a
Fe(CN) 3'
(M-C)
IrCl63-
(M-L)
2.357 ± 0.05b
(C-N)
Fe(CN)64’
wci6
(M-L)
2.26c
(M-C)
(C-N)
wci6'
(M-L)
2.31d
Ru(NH3)62+
(M-N)
Co (NH3)2+
(M-N)
(N-H)
2.114e
1.0109
(N-H)
(M-L)
Ru(NH3) 3+
(M-L)
2.173h
(M-N)
Co(NH3)3+
(M-L) 1.936f
(N-H) 1.0109
(M-L) 1.995h
aValues taken from ref. 102.
(N-H)
(M-L)
'Value estimated by adding 0.05 Á to value for IrCl62"(see
cValue in gas-phase from ref. 107.
'Value estimated by adding 0.05 Á to value for WCl6
eValue of M-N distance from ref. 108.
Value of M-N distance from ref. 109.
9Value of M-N distance from ref. 110
hEffective value is center of mass calculated from M-N and
Bond Length/Á
1.936a
1.191a
1.900a
1.138a
2.144f
1.0109
2.203h
2.104f
1.0109
2.163h
text) .
N-H distances.

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pua 9iow 9dW TEJPsMEjoo joj saxdojjua jbuotjbjo.1 jo jofd "I-t' Q-znbTj
V/aouD^Q -|-(«|
0

58
Resulting values of rotational entropies for the complexes
Table 4-7, with the values of the total standard gas-phase
AS1- (gas)°.
are given in
entropies,
Changes in Vibrational Entropy
The expression for qyjb is given in eg 4-9.
^vib
1
1-e ~x
4-9
Vibrational energy spacings are typically larger than kT and the
summation in eg 4-2 can not be replaced by an integral. Equation 4-9 is
given from a binomial expansion of eq 4-2. In eq 4-9 the term x is
hcu/kT, in which u is the frequency of the vibrational mode and c is the
speed of light. The vibrational thermal energy per degree of freedom
can be found by substituting eq 4-9 into eq 4-3. The result is given in
eq 4-10.
[E-E0] vib
4-10
Since the magnitude of vibrational energy spacings are typically close
to or larger than kT, the value of (E-Eo)vib some fraction of RT per
mol, per degree of freedom. Changes in vibrational frequencies that
occur on electron attachment cause a change in both qyib and (E-E0)yjb
and both terms on the right of eq 4-3 therefore contribute to ASj(vib)0.
Substituting the expressions for (E-E0)yjb and 3vib into etJ 4-4 gives an
expression for ASj(vib)0 (eq 4-11).
4-11
Equation 4-11 includes the summation over all normal modes in the

59
Figure 4-2. Plot of the entropy of a vibrational mode as a function of
the vibrational frequency.

60
oxidized and reduced species, the frequencies of which are included in
xR and xQ. The definitions of xR and xQ are the same as that given for x
in eq 4-7, but apply to the reduced and oxidized species respectively.
The vibrational characteristics of metal complexes suggests that
vibrational entropy changes can be significant in certain cases. In
Figure 4-2 vibrational entropy is plotted as a function of vibrational
frequency at 298 K. It can be seen that S^vib)0 increases dramatically
as the frequency of a vibrational mode decreases. For organometallic
and coordination compounds, vibrations associated with metal-ligand
skeletal modes are typically in the range of 100-700 cm"1. Shifts in
these frequencies, of the magnitude that occur for a change in formal
oxidation state at the metal center, can cause significant changes in
entropy per vibrational mode, especially at low frequencies. Moreover,
a non-linear molecule has 3N-6 vibrational modes (where N is the number
of atoms in the molecule). For MX6 octahedral complexes there are
therefore a total of 15 skeletal vibrations that enter into the
summation in eq 4-11.
Vibrational frequencies used to calculate the vibrational entropies
for the complexes considered in this chapter are given in Tables 4-2 to
4-4. The assumption is used throughout that the vibrational frequencies
reported, observed in solution and in the solid state, are the same as
their gas-phase values. Since a small dependency on the polarizing
nature of counter ions is observed for solid state spectra, solution-
phase data are used wherever possible. The only frequencies used that
are obtained from solid state spectra are for the IR active T1u modes.
These are the only IR active vibrations and account for 6 of the 15
possible skeletal modes for MX6 complexes and 12 of the 33 possible
vibrational modes in M(XY)6 complexes. The Raman active vibrations are
Alg, Eg and T2g. The T2u and Tlg modes are inactive. Frequencies for
these modes are either estimated or are obtained from the results of
reported force-field calculations (see Tables 4-2 to 4-4). The error

61
Table 4-2. Assignments of Vibrational Frequencies (cm~1) for
Hexachloride Metal Complexes.
A1
Aig
Eg
«3
T1u
>
T1u
«5
T2g
^6
T2u
IrCl62'*a
353
225
333
184
196
139b
IrCl63' 323
303
309
200
161
144
wci6a
437
331
373
160
182
129b
WCl6*'a
378
318
330
158
168d
127b
frequencies taken from ref. 111.
bThe T2 bend is infrared and Raman inactive; value obtained from
u6 = u5(2"1/2), see text.
frequencies taken from ref. 112.
hvalue from ref. 113.

62
Table 4-3. Assignments of Vibrational Frequencies (cm'1) for Hexacvano
Metal Complexes.
Fe(CN)63'»a
Skeletal M-C
u2
u4
u7
U9
U11
u13
Vibrations
E9
T
x1u
rp
T2g
i2u
390
324
511
95
102
to
XT
M-C-N
Vibrations
T19
u8
T1u
>
T2g
u12
T2u
351b
387
410
381b
C-N
Vibrations
"l
A19
^3
Eg
*6
T1u
2136
2136
2105
Fe(CN)64' Skeletal M-C
u2
u4
u7
u9
U11
u13
Vibrations
Aig
E
9
T1u
T1u
T2g
T2u
410
390
585
95
102
to
XT
M-C-N
Vibrations
«5
Tlg
>
T1u
>
T2g
T2u
350b
414
420
402b
C-N
Vibrations
O)
u3
E9
u6
T1u
2080
2048
2033
aAll frequencies taken from ref. 114.
bAll T1g and T2u modes are both infrared and Raman inactive; values given
are from the normal coordinate analysis in the reference in footnote a.

63
Table 4-4. Assignments of Vibrational Frequencies (cm'1) in Hexammine
Metal Complexes.
Ru(NH3)63+-a
Skeletal M-N u
Vibrations
1
*19
L1u
L1u
L2g
l2u
500
475
463
273
248
175c
Lig
L1u
2g
L2u
Ammonia
Rocking
Vibrations
788c
788c
788
788c
Ru(NH3)62+>a
Skeletal M-N u1 i>2
Vibrations A,_ E
ig 9
450 430
409d 170e 170e 120b
270e 270e 190b
ig
L1u
2g
2u
769c 769c
769c
Ammonia
Rocking
Vibrations
769

64
Table 4-4 continued.
Co(NH3)63+'a
Skeletal M-N
Vibrations
U1
Alg
u2
E9
u3
T1u
u4
T1u
u5
T2g
u6
T2u
494
442
475
331
322
228b
Tl9
T1u
T2g
T2u
Ammonia
Rocking
830c
831
830
830c
Vibrations
Co
(NH3)
2+.a
Skeletal M-N
Vibrations
ig
L1u
1u
L2g
l2u
357
255
325
192
187’
132c
ig
L1u
2g
l2u
Ammonia
Rocking
Vibrations
654c
654
654c
654c
aFrequencies taken from ref. 115.
kvalue for u6 obtained from u6 = i>5(2‘1/2), see text.
CT^ and T- rocking vibrations are infrared and Raman inactive and T2
value may be unavailable. Frequencies given are assumed to be the same
as the T1(J mode given in ref. 116.
dOnly available frequency, from ref. 117, others estimated.
eNo data available. Frequencies given represent estimated lower limits
(values for Cd(NH3)62+) and upper limits (values for Ru(NH3),3+) taken
from ref. 115.
fValue obtained from approximate narallel relationship between
variations in frequencies for Co3 and Co2+ complex.

65
limit placed on all estimated frequencies is ± 10%. The most
potentially serious error in the calculation of vibrational entropies
comes from the estimated frequency of the inactive T2u skeletal bending
mode. The frequency of this mode is typically in the region of 100 cm"1
or so and any uncertainty produces a large error in the vibrational
entropy (see Figure 4-2). For most of the complexes in Tables 4-2 to 4-
4 the skeletal T2u mode was obtained from the relationship u6 = i>5(2‘1/2).
The relationship is predicted theoretically and has been shown to
correctly predict values of u6 for some XY6 compounds in which the
central atom has a closed shell electronic configuration.118 For dn
octahedral transition metal hexafluorides, for which u6 is available
from combination bands or resonance phosphorescence spectra, the
relationship is generally observed to hold to within the error limits of
± 10% given here.
For Ru(NH3)62+ data for the frequencies of the skeletal modes have
not been reported, except for the T1u mode (see Table 4-4). The
frequencies given in Table 4-4 are estimations based on calculations and
observed frequencies for other hexaammine complexes of M+2 ions. In
addition to the skeletal modes given for the hexaammine complexes in
Table 4-4, frequencies are reported for the ammine ligand N-H rocking
vibrations. Unlike the skeletal modes, these frequencies are available
for Ru(NHj)62+.116 The N-H rocking vibrations are the only other
vibrations of low enough frequency to contribute significantly to the
vibrational entropy for these complexes. There are a total of 12 modes
(T1gf T1u, T2g and T2u) of which only the T1(J and T2g modes are infrared or
Raman inactive. These frequencies are observed at 831 cm"1 and 830cm"1
respectively for Co(NH3)63+, but only the infrared active T1u modes are
observed for the other complexes. It is assumed that the inactive modes
are of the same frequency within the error limits given. These
relatively high frequency modes only contribute a few cal mol'1 K"1 to
AS1- (vib)°.

66
Changes in Electronic Entropy
Electronic energy separations are usually large compared to kT. The
exponential term in eq 4-2 is therefore close to zero and qelec is
usually equal to the degeneracy of the ground electronic state. The
maximum possible degeneracy of an electronic state is given by the
product of the total spin and orbital degeneracies. The required
information is carried in the spectroscopic term symbol for the state.
Under the octahedral point group the orbital degeneracy is denoted by
the symbols A, singly degenerate; E, doubly degenerate; and T, triply
degenerate. The total spin degeneracy (multiplicity) is given by 2S+1
where S is the total spin angular momentum and is denoted in the
superscript preceding the orbital symbol. The spectroscopic term
symbols for octahedral complexes are derived purely from the symmetry of
the metal d orbitals in an octahedral ligand field. In reality, the
degeneracy of the electronic ground state of a particular complex can be
split in energy. The extent of the splitting depends on the structure
of the complex and the nature of the electronic state itself. The
ground state electronic degeneracy of the complex may therefore be less
than the value suggested by the spectroscopic term symbol, since it is
dependent on the thermal population of the energetically split states.
There are two principle effects that contribute to the splitting of
orbital degeneracies, spin-orbit coupling and distortions from perfect
octahedral symmetry.
Spin-orbit coupling. The coupling of spin and orbital angular
momenta of the d electrons results in a splitting of electronic
degeneracy. For A and E ground states there is no orbital angular
momentum and consequently no spin-orbit coupling. For T ground states
the orbital and angular momenta couple and the electronic degeneracy is
lifted. For complexes of the first transition series metal ions,
orbital splittings are typically in the range of 100 - 1000 cm'1
(~kT/2 - -5kT). The actual value depends on the metal, its oxidation

67
state, the value of the Racah electronic repulsion parameter (B), and
the magnitude of the ligand field (lODq). For second and third row
metals the effect is greater and orbital splittings are generally in the
range of 500 - 5000 cm'1.
Distortions from octahedral symmetry. Molecules that have orbitally
degenerate ground states have a tendency to physically distort to move
to a state of lower energy and lower symmetry, removing the orbital
degeneracy of the state. This statement is a simplified form of the
Jahn-Teller theorem.119,120 The effect is observed to occur for
octahedral metal complexes. For example, Ti(H20 ) 63+, which has
ground state is not purely octahedral and the t2g + eg orbitals are
split into a set of b1g, alg, b2g and eg states. The single electron
resides in the lowest energy blg orbital. Similarly, for ions such as
Cu2+, a pure octahedral ligand field would produce a degenerate Eg set
of orbitals containing three electrons. From experiment, the orbitals
are found to be split such that the unpaired electron resides in a state
of single orbital degeneracy. The magnitude of the orbital splitting is
typically in the range of about several hundred wave numbers up to about
2000 cm'1 (observed for Cu2+ complexes), and so are comparable to the
magnitudes of splittings due to spin-orbit coupling. For tris-chelate
complexes (D3 symmetry) a trigonal distortion is possible if the "bite
angle" of the ligand is not precisely 90°. In this case, the degenerate
t2g set (octahedral symmetry) is split into a set of A1 and E orbitals.
The Eg set in octahedral symmetry remains a doubly degenerate E set in
D3 symmetry. An example of the degree of trigonal splittings in
M(acac)3 complexes has been reported for Co (acac) 3.121 The crystal
structure of Co(acac)344 reveals an average O-Co-O bite angle of 97.3°.
From studies on the polarized crystal spectra of Co(acac)3 the 1A1 -> 1T1
transition was found to be split by the trigonal field into components
at 16200 cm’1 (1A) and 17000 cm'1 (1E);11 that is, a splitting of
800 cm’1.

68
The geometry of the complex in the gas-phase has not been reported.
The entropy of an electronic state can be evaluated from eq 4-3. In
the absence of a thermally accessible higher lying states, the entropy
of a ground electronic state is given by S = R In g, where g is the
degeneracy of the ground state. If thermal population of higher lying
states is possible, the entropy of the state must be considered in terms
of the thermal population of the split states; that is, the electronic
partition function (qeLec) must be evaluated. An orbitally split state
that can be thermally populated will also posess a thermal energy
((E-E0)e^ec) . This thermal energy must also be considered when
evaluating the entropy of the state, as defined by equation 4-3. An
example of the relationship between the entropy of an electronic state
and the splitting of the degeneracy of the state by an energy AE at two
temperatures is given in Figure 4-3 for the example of a 2E state. For
AE = 0 the entropy is given by S = R In g and for a 2E state this is
equal to R In 4 (2.75 cal mol'1 K'1). The splitting of the state is
shown in Figure 4-3 (a). As AE increases the value of qelec, given by
qelec = 2(1 + e("AE/RT>), rapidly decreases and R In qelec rapidly
approaches a value of R In 2 (1.38 cal mol’1 K’1) as shown in Figure 4-3
(b). For AE > 0 (E-Eo)eiec i-ncreasesf reaches a maximum value, and then
approaches 0 as Ae becomes so large that the upper state is no longer
thermally accessible. The value of (E-Eo)eiec ^"s 9^-ven
[ (e( 4E/RT)) / (1 + e('AE/RT))] AE and has been shown by Lias and Ausloos92c to
reach a maximum of “0.2 kcal mol"1 for a 2E state. The contribution to
the entropy is given from (E-EQ)elec/T, which is also shown in Figure 4-3
(b). The overall effect on the entropy of the state is that it also
converges on the value of R In 2, but retains a significant amount of
its orbitally degenerate value, even for orbital splittings as high as
800 cm'1. It can be seen that at 350 K, relative to 298 K the entropy
of the state is less diminished from its orbitally degenerate value for
the same orbital

69
(a)
t
Í
U
i
(b)
= 350 K
= 298 K
Figure 4-3. The electronic entropy of a 2E state, (a) The electronic
state split by an energy AE; (b) Plot illustrating the contributions of
the terms in eq 4-3 to the entropy of a 2E state, as a function of the
splitting energy AE.

70
splitting. At absolute zero no thermal population of higher lying
states is possible and the entropy of the state is given by the
degeneracy of the lowest lying state.
Assessing the entropies of electronic around states. The combined
effects of spin-orbit coupling and distortions from octahedral symmetry
give a characteristic splitting of electronic degeneracy for a
particular metal complex that is dependent on the metal ion, its
oxidation state and the nature of the coordinated ligand. Since the
energy spacings are typically on the order of magnitude of kT, a range
of states in the electronic manifold can be thermally populated,
depending on the resulting energy spacings and the temperature. The
increasing population of higher lying states with temperature is
particularly manifest in the temperature dependence of the magnetic
susceptibility of transition metal complexes.122
In Table 4-5, estimates are given for the change in electronic
entropy for the redox couples containing the octahedral ions considered
here. For the complexes with A and E ground states, the orbital angular
momentum is quenched and so the electronic degeneracy is not split by
spin-orbit coupling. For A ground states, therefore, the entropy of the
electronic state was estimated by assuming that the electronic partition
function is equal to the spin degeneracy. For E ground states, the
orbital degeneracy may be split by distortions from octahedral symmetry.
The entropy of the state depends on the thermal population of the upper
state. As shown in Figure 4-3, for typical values of the energy
separation between the states, the upper state can be accessible at
ordinary temperatures. Since the energy spacings between the split
states are not known, the entropy of E states was estimated from the
average value obtained from the spin degeneracy and the total degeneracy
of the state. For T states, the splitting pattern becomes more complex
due to the effect of spin-orbit coupling, especially for first
transition series metal ions. The lowest energy manifold for electronic

71
Table 4-5. Electronic Entropy Changes For Redox Couples.
Redox Couple
Change in
Electronic
Ground State ASj(elec)0,a
Fe(CN)63'/4‘(soln)
IrCl62'/3’(soln)
WC160/' (soln)
Co (NHj) 63+/2+ (soln)
Ru(NH3)63+/2+(soln)
Sc (acac) 30/' (gas)
Ti(acac)30/f‘ (gas)
V(acac)30/" (gas)
Cr (acac) 30/' (gas)
Mn (acac) 30/" (gas)
Fe (acac) 30/' (gas)
Co (acac) 30/‘ (gas)
1,
'1
-1.78 ± 1.78
-1.78 ± 1.78
-0.58 ± 2.20
2.48 ± 2.48
-1.78 ± 1.78
1.78 ± 1.78
0.41 ± 3.98
0.58 ± 2.19
1.15 ± 0.69
-0.34 ± 0.69
-0.87 ± 2.71
2.48 ± 2.48
aValues are AS0 in cal mol*1 K"1. Calculated for ox + e’ -* red in the ion
convention. Entropy of the free electron is not included.

72
states split by spin-orbit coupling can have a lower degeneracy than the
spin degeneracy122 and a realistic evaluation of the range of values of
the electronic partition function is difficult to estimate. For the
complexes that have T ground states in Table 4-5, the electronic entropy
was estimated from a value of the partition function taken as the
average of 1 to the maximum degeneracy of the state, as given by the
appropriate term symbol. Estimates of electronic energy spacings, and
hence the electronic partition function, can be obtained from matching
the observed temperature dependence of the magnetic susceptibility of a
complex to the theoretical temperature dependence, derived from
theoretical energy spacings, but such data are scarce.
Comparison of Solution-Phase and Gas-Phase Entropy Changes for Some
Redox Couples Involving Octahedral Metal Complexes
Entropy Changes for Solution-Phase Redox Couples
The experimental method for obtaining entropy changes for half-cell
redox couples involves the use of cyclic voltammetry in a non-thermal
cell arrangement that permits the temperature of the half-cell
containing the redox couple of interest to be varied, while the
temperature of the other half-cell, containing the reference electrode
is held constant. The method provides a simple means to evaluate the
difference between the absolute ionic entropies of the reduced and
oxidized halves of the couple (ASrc°), given in eq 4-12.
ASr°c - Sr°ed - S0°x 4-12
Interpretation of entropy changes for redox couples involving
coordination complex ions to date has centered on the difference in the
degree of solvation of the oxidized and reduced forms of the ions in the
redox couples. Changes in solvation entropies are expected, since
reduction of a complex is accompanied by a change in the charge on the

complex ion. However, dielectric continuum models have not provided an
adequate description of observed ASrc° values. In particular, the
anomalous entropy changes associated with Co(III)/Co(II) couples (in
comparison to analogous Ru(III)/Ru(II) couples) have evaded satisfactory
quantitative explanation. By calculating intramolecular entropy changes
for redox couples involving coordination complexes by using statistical
mechanics, the intramolecular and solvent contributions to ASrc° can be
estimated.
Several AS ° values have been determined by various workers and a
rc J
selection of the results for various redox couples are given in Table
4-6. The solvent for all redox couples in Table 4-6 is water. Also
given in Table 4-6 are the theoretical values of ASpc° predicted by the
Born equation (ASBorn°). The Born equation124 is based on a purely
electrostatic model and can be used to obtain the change in free energy
and entropy when a charge is transferred from a conducting sphere in a
vacuum to an identical sphere in a medium of dielectric constant e (eqs
4-13 and 4-14).
4-13
q2 /dine\
2zTe\dlnT/p
4-14
In eqs 4-13 and 4-14, q is the charge on the conducting sphere and e is
the dielectric constant of the medium. When the medium is water at 25°C
and the spheres are ions of absolute charge ze, eqs 4-13 and 4-14 can be
written in the convenient forms of eqs 4-15 and 4-16.
AGB°orn - -163.89
kcal mol"1
4-15

74
Table 4-6. Experimental and
Theoretical
Entropies
for Redox Couples
Redox Couple
AS °'a
rc
As„ °*a
Born
- AS 0
abBorn
A(M_L^g.)
) Distance/A
Ru(NH3)63+/2+'c
18.5
14.6
3.9
0.040e
Os(NH3)63+/2+'b
18 ± 0.5
14.6
3.3
Co(NH3)63+/2+'d
45
14.6
30
0.178e
Ru (en)33+/2+,b
13 + 0.5
13.0
0
Co(en)33+/2+,b
37 + 2
13.0
24
Ru(H20 ) 63+/2+>c
38 ± 3
14.6
23
Co(H20)63+/2+'d
60
14.6
45
Fe(H20)3+/2+'b
43
14.6
28.4
Ru(bipy)33+/2+>c
1 ± 2
7
-6
-0.048f
Fe(bipy)33+/2+'c
2 ± 2
5
-5
Co (b ipy) 33+/2+»c
22 ± 3
7
14
Fe(CN)63'/4'«c
-41.5
-15
-27
-0.036e
aAll values given in cal mol'
1 K'1.
hoata from ref.
103.
cData from ref.
104.
dFrom ref. 105 (value estimated by authors).
eData from Table 4-1.
fData from ref. 123.

75
AS
o
Born
-9.649
cal mol_1 K 1
4-16
The Born equation is most successfully applied to large and
approximately spherical ions of low charge, and where specific
solute/solvent interactions are absent. For these ions, the effect of
changes in size of the ion with changes in the oxidation state of the
metal and the effect of dielectric saturation are both minimized. It
should be noted that for the reduction of a complex bearing a positive
charge the sign of Asgorn0 is positive. For neutral complexes and those
bearing a negative charge, the sign of ASBorn° is negative. A more
positive entropy can be associated with ions of lower charge, since
there will be less "ordering" of the surrounding solvent molecules.
Comparing the experimental and theoretical entropy changes for the
redox couples in Table 4-6, it is seen that there is generally a poor
agreement between the two values. However, the theoretical value serves
as a reference point to which the experimental values can be compared in
the absence of specific solute-solvent interactions. The sign and
magnitude of the deviations of experimental results from ASBorn° provide
information about the nature and the extent of the changes in specific
solute-solvent interactions that occur on reduction of a particular
metal complex. The difference between ASrc° and ASBorn° for each couple
is included in Table 4-6 for this purpose.
It is particularly interesting to note in Table 4-6 that for the
couples Ru(bipy)3+/2+ (where bipy = 2,2' -bipyridine) and Fe(CN)63'/4', for
which the nature of the M-L bonding is more complex than simple a
bonding, that the value of Asrc° - AsBom° is negative. For each of these
couples the average M-L bond length in the reduced form of the complex
is shorter than in the oxidized form. The arguments generally invoked
to explain this phenomenon is that the energies of the metal orbitals
are raised in the reduced form of the complex, which provides a better

76
energy match with ligand tt orbitals, and subsequently an overall
increase in the degree of (M-L) bonding. A related argument was used by
Yee and Weaver to account for the negative value of ASrc° - ASBorn° for
the Ru(bipy)33+/2+ couple.10^ It was suggested that two competing effects
are in operation. The water molecules close to the ruthenium center,
including those surrounding the ligands, will be less polarized and
therefore less "ordered" in the lower oxidation state, giving rise to a
positive contribution to ASrc°. However, the water molecules adjacent
to the bipyridine rings may experience an increase in polarization in
going to the Ru(II) state since the added t2g electron will be
significantly delocalized around the aromatic rings, acting to increase
their net charge density. The latter contribution would give a negative
contribution to ASrc°. An opposite effect was used to describe the
anomalously large value of ASrc° for Co(bipy)33+/2+. The Co(III) -»
Co(II) reactions involve the electronic conversion t2g6 -» t2g5 eg2, which
should minimize the extent of electron delocalization in the reduced
state and therefore discourage any increase in solvent polarization in
the vicinity of the bipyridine rings. Further, the expansion at the
metal center was suggested to lead to an especially large decrease in
the polarization of nearby water molecules. It seems that the arguments
for the negative value of Asrc° - ASBorn° for the Ru (bipy)33+/2+ couple are
not without merit, since an alternative explanation is difficult to
conceive. The explanation for the Co (bipy )33+/2+ couple may be
questionable, however, since the large difference of approximately 22
cal mol"1 K"1 between the Ru (bipy)33+/2+ and Co(bipy)33+/2+ couples is
consistently found for other couples involving reductions at Ru(III) and
Co(III) centers where only M-L a bonding is possible. It seems that
whatever mechanism is operative in causing a negative value of ASrc°
- ASBorn° for the Ru (bipy )33+/2+ couple is also operative for Co(bipy)33+/2+
and alternative explanations of the large observed differences in ASrc°
must be considered.

77
Intramolecular Contributions to ASrc°
Single ion hydration entropies have been obtained for many monatomic
and polyatomic ions by evaluating the entropy change for the
transference of a gas-phase ion M of charge n to the solution phase
according to the reaction Mn(gas) -» Mn(aq).125*128 The value of AS0 for
the reaction is given by eq 4-17
4-17
ASj (hyd) ° - Si (gas) ° - S* (aq) ° + 6.35 cal mol "1 K'1
The value of 6.35 cal mol’1 K'1 (R In 24.41) arises from the different
standard states for the gas-phase and the solution phase. The value of
S1- (gas)0 and Sj(aq)° for a particular ion are typically quite different,
the value of Sj(aq)0 being smaller and often negative. Translational
freedom is restricted and it is uncertain how rotational motion will be
affected. Also polarization of the solvent may contribute greatly to
the difference in entropy of an ion between the two phases. Although
AS^aq)0 data are available for a large number of polyatomic ions, there
are apparently no reports on comparisons made between ASj(gas)0 and
ASj (aq)° for ionic species in redox couples. The results of the
calculations that yield the gas-phase entropies of the octahedral
complexes considered in the present work are presented in Table 4-7.
From the results of the calculations it can be seen that S-(trans)0 is
the same for the oxidized and reduced species, and that S-(rot)0 is
within ±0.5 cal mol’1 K'1 (Figure 4-1). It can be anticipated that
these terms will also remain constant between the oxidized and reduced
species in solution. Much larger differences in entropy can potentially
arise from S^vib)0 and Suelee)0, and the calculated gas-phase values
should remain unchanged between the two phases. In considering the
total difference in entropy for a redox couple involving octahedral
transition metal ions in solution, therefore, eq 4-18 will apply.

78
ASt°c - AS^vib) ° + ASi(elec) ° +AS°olv 4-18
In eq 4-18, ASsoly° is the difference in the entropy of solvation of the
ions in the redox couple. There are two situations where the
contribution of ASsoly° to ASrc° can be separated from ASrc° so that the
contributions from ASj(vib)0 and ASj(elec)0 may be estimated. For ions
of large radii, ASsoly° in water is predicted by the Born equation (4-16)
to be small and therefore ASrc° = ASj(vib)0 + ASj(elec)0. Also, when
comparing two redox couples of different metal ions coordinated by the
same ligand, and undergoing the same change in oxidation states, Assoly°
is constant and AASrc° = AAS^vib)0 + AASj(elec)0.
It is illuminating to compare the results of the gas-phase
calculations, which are given in Table 4-7, to the experimental results
obtained in aqueous solution, which are given in Table 4-6. For the
ions that form the redox couples Ru (NHj) 63+/2+, IrCl62"/3', WC160/" and
Fe(CN)63*/4' the difference in gas-phase entropies is small and therefore
only ASsolv° will contribute to ASpc. For the Co(NH3)63+/2+ couple
ASjfgas)0 = 17.8 cal mol"1 K’1. The origin of the comparatively large
value of ASj (gas)0 can be traced to the difference in spin states
between the oxidized and reduced species. In Co(II) complexes the M-L
bonding is significantly weakened relative to Co(III) complexes as a
result of the doubly occupied antibonding eg metal based orbitals in the
Co(II) state. As a result, the skeletal vibrational modes are shifted
to substantially lower frequencies and a large increase in vibrational
entropy results. The greater electronic degeneracy of the Co(II) state
also gives rise to a significant increase in ASj(elec)0 (Table 4-6).
The change in spin state for Co(III)/(ll) couples has been observed
to greatly shift skeletal vibrational frequencies for other octahedral
and pseudo-octahedral complexes of cobalt. For example, for tris
complexes of 2,2'-bipyridine and the related ligand 1,10-phenanthroline

Table 4-7. Gas-Phase Standard Molar Entropies of Octahedral Ions
Complex
Sj (vib)0,a
Sj (rot)0,3
Sj(elec)0
ia
Sj(trans)3
Sj (gas)0,a
IrCl62"
Skel.
30.6
+
0.7
25.0
1.8
+
1.8
43.9
101.3 ± 2.5
IrCl63"
Skel.
30.5
±
0.3
25.2 ± 0.3
0
43.9
99.6 ± 0.6
wci6
Skel.
30.0
±
0.6
24.9
2.8
43.8
101.5 ± 0.6
wci6-
Skel.
31.2
±
0.6
25.0 ± 0.3
1.8
±
1.8
43.8
101.8 ± 2.7
Fe(CN)63"
Skel.
34.6
±
0.6
24.7
1.8
+
1.8
42.0
115.8 + 3.4
M-C-N
12.7
+
1.0
C-N
<0.01
Fe(CN)64"
Skel.
34.3
+
0.6
24.5
0
42.0
112.1 ± 1.6
M-C-N
11.3
±
1.0
C-N
<0.01
Ru(NH3)62+
Skel
25.4
±
3.8
22.6
0
41.6
92.4 ± 4.8
NH3(r)
2.8
±
1.0
Ru(NH3)63+
Skel.
21.5
±
0.7
22.5
1.8
+
1.8
41.6
90.0 ± 3.5
NH3(r)
2.6
±
1.0
Co(NH3)63+
Skel.
17.9
±
0.6
22.0
0
41.1
83.2 ± 1.4
NH3(r)
2.2
±
0.8
Co(NH3)62+
Skel.
30.5
±
1.2
22.5
2.5
+
2.5
41.1
101.0 ± 4.9
NH3(r)
4.4
±
1.2
aAll values are given in cal mol"1 K"1.

80
(1,10-phen) complexes of the same metal ion have similar M-L vibrational
frequencies. For Fe (bipy )33* infrared active M-N vibrations are
observed at 384 and 367 cm'1.129 For Fe(bipy)32+ these frequencies are
shifted slightly to 386 and 376 cm'1 respectively.129 For
Co(1,10-phen)3+ similar frequencies to these are observed at 378 and 370
cm'1,130 but for Co(bipy)32+ are shifted to substantially lower
frequencies at 266 and 228 cm'1.129 Large contributions to vibrational
entropy can be generally expected for cobalt couples that undergo the
same change in spin state, although a complete set of data for all the
vibrational frequencies that are different between the oxidized and
reduced species are required to quantitatively evaluate ASj(vib)0. For
all the redox couples involving Co(III)/Co(II) reductions in Table 4-6
the same spin change is involved and values for ASrc° are constantly 22-
25 cal mol'1 K'1 higher than the corresponding Ru(III)/Ru(II) couples.
The difference in the values of ASj(gas)0 for the couples Co(NH3)63+^2+
and Ru(NH3)63+/2+ obtained from the calculations in the present work is
15.4 cal mol"1 K'1. The result demonstrates the importance of
intramolecular entropy changes for Co(III)/Co(II) redox couples, and
offers a feasible explanation of the large differences in ASrc° for the
Ru(III)/(II) and Co(III)/(II) redox couples studied in aqueous solution.
The Relationship Between The Free Energy and Enthalpy of
Gas-Phase Electron Attachment to MfacacK and M(hfac)3 Complexes
The electron attachment energies quoted for the M(acac)3 and
M(hfac)3 complexes in the present work are free energies (AGg0) obtained
at 350 K. The data would serve a wider range of applications in
thermochemistry if values of AG ° and AH 0 could be obtained at other
temperatures. It is particularly useful to obtain AHa° data at 0 K and
at 298.15 K. Values for AHa° at 0 K are the electron affinities of the
complexes, which may be used and compared with other electron affinity

81
data. Values for AHg° at 298.15 K can be readily combined in energy
cycles with compiled data for other processes. The relationship between
AGg° at an experimental temperature (Tgxp) and AHg° and AGg° at a
different temperature (T) is given in equations 4-19 and 4-20
Texp
AGa°(T) - AGa°(Texp) + ASa°[Texp-T] - f Cp (M) dT + fcp(M‘)dT 4-19
T T
Texp T^jjp
AHa°(T) - AGa°(Texp) + TexpASa - I Cp (M) dT + f Cp(M')dT 4-20
T T
It is often assumed that temperature dependence of AHg° and ASa° for
electron attachment or ionization of a neutral molecule is negligible.
For example, for electron capture by a species M to form M"; AGg°(0 K) =
AHg° (0 K) = the electron affinity of (M), and equation 4-20 has been
used by Kebarle to quote electron affinities of organic compounds,
neglecting the integral terms. Lias and Ausloos920 have explored the
validity of this assumption by performing statistical thermodynamics
calculations on several organic and inorganic compounds from
spectroscopic data. As shown above, and stated more explicitly by Lias
and Ausloos, the difference in translational and rotational thermal
energy between a species M and its ion (M+ or M') is negligible.
Differences can only arise from (E-E0)vjb and (E—EQ)eiec* Under the
convention the volume of the electron gas is zero and so for electron
attachment AP =AV = 0. Therefore, C = C and Ae = AH. Lias and
V p
Ausloos showed that from the compounds they studied, the largest
difference between the adiabatic ionization potential (0 K) and the
enthalpy of ionization of enthalpy at 350 K arose for ethylene, which
_ ^ *
was 0.22 kcal mol less exothermic at the higher temperature.
In order to determine AHg°(T) for the metal complexes in this study
ASg° must be known. Any uncertainty in this value will lead to the
largest error in AHg°(T), since the absolute magnitude of TexpASg° in eq

82
4-20 can be expected to be significantly greater than the absolute
magnitude of the sum of the integral terms. From the calculations given
above for pairs of octahedral transition metal complex ions that form
redox couples (Table 4-7), it can be seen that where the acceptor
orbital is a non-bonding metal t2g, ASg° is ± 3 cal mol"1 K’1. This value
is comparable to the organic compounds for which ASg° has been
determined experimentally and can be expected to apply for electron
capture by the M(acac)3 and M(hfac)3 complexes of Sc, Ti, V and Fe.
From the results of the calculations given in Table 4-7, for the gas-
phase Co(NH3)63+/2+ couple a larger value of ASa° (17.8 cal mol’1 K"1) was
obtained, which was attributed to a consequence of the difference in d
electron configuration between the oxidized and reduced forms. The same
difference in electronic configuration is expected to exist for the
Co(acac)30/" (g) and Co(hfac)30/" (g) couples and ASa° may also be in the
range of 20 cal mol’1 K’1.* For the acac and hfac complexes of Cr and Mn
electron capture results in the following changes in d electron
configuration; Cr t2g3 -» t2g3 eg1; Mn, t2g3 eg1 -» t2g3 eg2. In each case the
additional electron is accommodated in the antibonding eg set and ASg°
may be in the range of 0 - 20 cal mol’1 K*1.
Conclusions
The results of the calculations presented here demonstrate the
importance of intramolecular entropy changes that occur on electron
attachment to coordination complexes. For solution-phase redox couples,
intramolecular entropy changes are generally smaller than the entropy
change occurring in the surrounding solvent. However, in special cases
*It is not profitable to attempt similar calculations directly for
M(acac)3 and M(acac)3' complexes. There is considerable disagreement in
the literature concerning the interpretation of the rather complex
infrared and Raman spectra for M(acac)3 complexes.

83
such as the Co(III)/(II) couples considered here, intramolecular entropy
changes may contribute significantly to the total entropy change for the
redox couple, even for ions of quite small radii. In the case of redox
couples involving large ions such as Co(bipy)33+/2+ differential
solvation effects are expected to be relatively small and ASrc° can
probably be attributed almost entirely to an intramolecular entropy
change. For example, ASrc° for [Fe(bipy)3]3+/2+ and [Co(bipy)3]3+/2+ are 2
cal mol'1 K'1 and 22 cal mol’1 K"1 in water, respectively. Although
extensive calculations of the vibrational partition functions cannot be
carried out for these ions due to the lack of spectroscopic data, the
-20 cal mol'1 K*1 difference in the ASrc° values is understandable in
view of the changes in M-N stretching (and presumably bending
frequencies) that occur for these two couples. Essentially no change in
M-N vibrational frequencies occurs for [Fe(bipy)3]3+/2+ while the
frequency change for [Co(bipy)3]3+/2+ couple amounts to an average of
-130 cm'1.
The insight gained from the calculations for intramolecular entropy
changes has enabled rough estimates to be made for the entropy changes
that occur for gas-phase electron attachment to the transition metal
/3-diketonate complexes investigated in this study.

CHAPTER 5
METAL-LIGAND BOND ENERGIES AND SOLVATION ENERGIES
FOR GAS-PHASE TRANSITION METAL TRIS(ACETYLACETONATE
COMPLEXES AND THEIR ANIONS
Introduction
There have been several attempts to determine the average
homolytic and heterolytic M-O bond energies in M(acac)3 complexes. The
most reliable are obtained through a thermochemical cycle based on the
enthalpy of hydrolysis of the complexes, obtained by using reaction
calorimetry. In the auxiliary thermochemical data required in the
cycle, the value for the homolytic bond enthalpy of the enolic O-H bond
in acetylacetone introduces the greatest uncertainty, since no
experimental data is available. From the results of thermal gas-phase
charge-transfer reactions involving acac' ions presented here, and the
proton affinity of acac" previously reported, a new estimate can be made
of this bond energy. From the original reaction calorimetry data,
better estimates can then be made for the average M-O homolytic and
heterolytic bond energies for M(acac)3 complexes. This data, combined
with the gas-phase electron attachment data for the M(acac)3 complexes
and the free gas-phase ion, leads to the average heterolytic bond
energies in the corresponding M(acac)3" ions.
Several of the M(acac)3 complexes for which electron attachment
data were obtained also exhibit reversible electrochemical behavior for
one electron reduction. From E^2 data, estimates can be made of single
electrode potentials. Comparison with the gas-phase data leads to the
change in solvation energy for M(acac)30/" couples. Reliable data for
solvation energies of complex metal ions are very scarce, yet are
84

85
essential for a complete understanding of the thermodynamics of redox
processes at coordinated metal centers. Consideration of the relative
contributions of the changes in solvation energies and bond energies
that occur for electron attachment to M(acac)3 complexes provides an
overall appreciation of how ionization potentials of M+3(g) ions are
related to the magnitude of a particular M(acac)30/' redox couple.
Electron Attachment Energy Relationships
The general thermochemical cycle in Figure 5-1 is the basis for
most of the thermochemical results presented in this report. The cycle
shows the general thermochemical relationships between thermodynamic
functions Ax for M-L bond formation or solvation of a complex and
electron attachment thermodynamics (AXg°) for a metal ion in essentially
three physically different environments (reactions a, b and c) at a
given temperature. A cycle of this type and crude estimates of the
various thermodynamic quantities were discussed by Buckingham and
Sargeson some 25 years ago.35 In reaction (a), electron attachment is
to a metal ion M with charge z in the free gaseous state, Mz(g). In
(b), electron attachment is to the gas-phase complex [MLy]n(g) of charge
n in which the metal ion M is equivalently ligated by anionic ligands
(L"). In (c) the solvated metal complex is reduced to [MLy]n_1 (soln) .
For the M(acac)3 complexes considered here, L=acac, Y = 3, z = +3, and
n = 0.
In the upper part of Figure 5-1, labelled I, the difference in
AXg° for the electron attachment reactions (a) and (b), given by
AXg°[Mz(g) ] and AXa°[MLyn(g) ] , are thermochemically related to the
difference in Ax° for heterolytic cleavage of the the metal-ligand bonds
for the oxidized and reduced form of the complex, AXhet°[(M-Ly)n] and
AXhet°( (M-Ly)(n'1)). A similar cycle can be used to derive AAXhom°( (M-Ly) ]
values for homolytic bond dissociation.

AXa° Mn(g)
(a) Mz(g) + (YxL“)(g) + e
AXhet° (M-U)n
(b) MLYn(g) + e'
AXa°(MLYn(g))
AX„,V°(MLV")
(c) MLYn(soln) + e'
AXa°(MLYn(soln))
M("1)(g) + (YxL-)(g)
AXh MLY("-'>(g)
AX^/CMLy'"-”)
MLY^”"(soln)
Figure 5-1. Thermochemical cycle relating thermodynamic functions Ax for electron attachment
processes (reactions a, b and c) and heterolytic bond energies and solvation energies for the
complexes MLy and MLy’.

87
In the part of the cycle labelled II the difference in AXa° for the
electron attachment reactions AXa°[MLyn(g) ] and AXa°[MLyn( soln) ] is
thermochemically related to the difference between AX° for solvation of
the oxidized and reduced forms of the complex (AXgotv°[MLyn] and
AXsolv°tMLY Experimental results for reaction (b) usually involve the
ionization of a neutral or electron attachment to a neutral. To
incorporate the energies for these processes into thermochemical cycles,
the values must be determined under thermal conditions. Such data can
be obtained by using mass spectrometry through studies of electron-
transfer equilibrium reactions and are often used to estimate the
adiabatic ionization energies or the electron affinities of polyatomic
species (these quantities are strictly the differences between the heats
of formation of the neutral and its ion at 0 K) as discussed in chapter
3. The method can be applied equally well to reactions involving
positive or negative ions, but such data for metal complexes is scarce.
Vertical ionization data are more widely available for volatile metal
complexes from studies of ionization appearance potentials and
photoelectron spectroscopy (PES) .56.131.132 The energy difference between
the adiabatic and vertical processes can be relatively small if the
geometry of the neutral is similar to that of the ion. For example, the
adiabatic ionization energy for ferrocene has recently been estimated as
6.69 eV by FTICR133 (Mautner134 suggests 6.81 eV from pulsed high
pressure mass spectrometry studies), while the vertical IP value
obtained from PES is 6.88 eV.135
Significant differences between adiabatic and vertical energies
may arise, however, when geometry changes upon electron attachment or
ionization are significant, and such substantial rearrangements are
common in transition metal complex redox chemistry. For example, the
adiabatic ionization energy of manganocene is '6.2 eV, 136,133 while the
vertical ionization energy obtained for the high-spin state by PES is

88
17p
7.0 eV. For metal complexes, therefore, vertical ionization data can
only be used in thermochemical cycles such as Figure 5-1 for those cases
where it is known, or can be reasonably assumed, that the geometries of
the neutral and the ion are not too dissimilar. It should be noted that
even if the 0-0 transition energy (the adiabatic energy) can be obtained
from the PES spectrum, a statistical mechanical calculation must be used
to derive enthalpy, entropy, and free energy changes at a given
temperature. Spectroscopic data needed for such calculations are often
unavailable or incomplete for transition metal complexes. On the other
hand, electron-transfer equilibrium studies provide data that can be
used directly in thermochemical calculations involving ionizations and
electron attachments near room temperature.
Combining gas-phase electron attachment energies with other
thermochemical data. In order to combine thermal gas-phase electron
attachment energy data for M(acac)3 complexes with other thermochemical
data it is useful to know the temperature dependence of Kgq (eq 2-2)
since such data leads to values of As ° and Ah °. Estimates of AG ° at
ad a
other temperatures can then be made. From the conclusions drawn from
chapter 4 concerning the magnitudes of ASa° for gas-phase coordination
compounds, a maximum value of ASa° = 20 cal mol'1 K'1 for the reaction
Co(acac)3(g) + e' -» Co(acac)3'(g) is assumed. The value for AHg° at 298
K is *7 kcal mol"1 higher than AGg° at 350 K (assuming AHg° is
independent of temperature). For the other M(acac)30/* couples where
less change in vibrational and electronic entropies occur, ASg° should
be smaller and similar to the values reported for organic compounds.
Values for the total metal-ligand heterolytic bond dissociation
enthalpies for M(acac)3 complexes (AHhet°[M-(acac)3)) of the first
transition metal series are found to be *1300 kcal mol'1 (see discussion
below). Since values of AGa° at 350 K and AHg° at 298 K for M(acac)3
complexes may differ by several kcal mol'1 in the worst case, the
percentage error introduced into derived values of AHhet°[(M-(acac)3*) ]

89
using the approximation AGa° (350 K) = AHa° (298 K) is small, since these
bond enthalpies have values in the range of “600-650 kcal mol’1 (see
below). When quoting an average energy per M-0 bond, AXhet°(M-0), the
error introduced by assuming AGg0 = AHg° is probably < 1 kcal mol’1 for
all cases .
As discussed above, throughout this dissertation the stationary
electron convention is adopted, which assigns a heat capacity and an
entropy of zero to the free electron. Under this convention the values
of AHa° for monoatomic ions at O K apply at all temperatures, since the
heat capacities of Mz and M(z'1) are always equal. Therefore, values of
AHa° M+3(g) are given by the negative value of the third ionization
potential for the metal. The stationary electron convention is adopted
to maintain consistency with the original AGg° values quoted for the
organic reference compounds on which the results presented in this
dissertation are based.
From cycle II of Figure 5-1, AGg° M(acac)3(g) data can be compared
with AGa° for the same process in solution to yield the difference
between the solvation free energies of a M(acac)3 neutral and its anion.
Values of AGa° M(acac)3(soln) can be estimated from electrochemical E1/2
values for M(acac)30,/* couples (see discussion below). Assuming
AGa°[M(acac)3(g)] data at 350 K is valid at other temperatures again
introduces an approximation, but using the upper limit of "20 cal mol’1
K’1 for Asa°, the error introduced in quoting values of
AAGsolv°[M(acac)30/’] at 298 K is again typically < 1 kcal mol*1.
In the thermochemical cycle used in this work to obtain values for
the bond dissociation enthalpies for M(acac)3 and M(acac)3* complexes a
value for AHa° at 298 K for acac1 radical is needed. The value obtained
from the gas-phase studies is a free energy, but ASa° is expected to be
typically small as observed for other organic compounds, especially
since the geometries of acac- and acac’ are probably quite similar.

90
Homolvtic and Heterolvtic M-O Bond Enthalpies in M(acac),(q)
Complexes and M(acac)-,'(g) Ions
The difference in the total heterolytic or homolytic metal-ligand bond
dissociation enthalpies between any M(acac)3 complex and its negative
ion can be obtained from the relationships in eg 5-1.
AAHhet°[M“(acac>30/'] s AHhet°[M-(acac)3] - AHhet°[M-(acac)3']
= AHa°[M+3(g)] - AHa°[M(acac)3(g) ] 5-1 (a)
AAHhom°rM-30/'] H AHhom° tM_ (acac) 31 " AHhom0[M-(acac)3']
= AHa°[M(g)] - AHa°[M(acac)3(g) ] 5-1 (b)
Values for the electron attachment energies required for eq 5-1 are
given in Table 5-1. Before deriving the average bond dissociation
enthalpies for the gas-phase M(acac)3' ions by using eqs 5-1 (a) and 5-1
(b), the available data for the corresponding neutral bond enthalpies
was critically assessed. Inaccurate assumptions made in the literature
derivations required us to generate new experimental data and thereby
revise the published enthalpies as discussed in the following.
For M(acac)3 complexes the average homolytic metal-oxygen bond
enthalpy, AHhom°(M-0), can be found from the thermochemical cycle in
Figure 5-2. The relationship between the various thermochemical values
is given in eq 5-2.
AHhom°(M-°) = 1/6 < 3AHf°(Hacac (1) ) + 3AHvap°(Hacac) + 3AHhom°(H-acac)
+ AHsub°(M> ” AHf°[M(acac)3(c)] - AHsub°[M(acac)3] - 3/2AHf°[H(g) ] ?-2
In Figure 5-2, AHvap°(Hacac) is the enthalpy of vaporization of
acetylacetone and AHsub°[M(acac)3] and AHsub°(M) are enthalpies of
sublimation of M(acac)3 and the metal M, respectively. The relationship

3D(H-acac)
-3/2 AH,°(H,g)
3/2 H2(g) + M(acac)3(g)
AHlub0(M(acac)j)
M(acac)3(c)
AHf°(M(acac)3)
3 H—acac
(enol)(g)
M(g)
AH °(Hacac)
AH.ub°(M)
3 Hacac(l)
M(c)
3 x AHf°(Hacac)
M(c) + 15 C(c) + 3 02(g) + 10.5 H2(g) 15 C(c) + 3 02(g) + 12 H2(g)
VO
Figure 5-2. Thermochemical cycle used to determine the enthalpies of formation of M(acac)3 complexes.

92
Table 5-1. Free Energies of Electron Attachment (kcal mol'1) to
Hlacacl-, complexes and Enthalpies of Electron Attachment to Free M*3 (a)
ions ana M(q).
M
AGa°[M(acac)3(g)]a
AHa°[M+3(g)]b
AHa°[M(g);
Ti
< 0
-633.53
-5(5)
V
-24.9
± 0.5
-675.45
-12(5)
Cr
-20 ±
1
-713.5
-15(1)
Mn
-59 ±
3
-775.9
> 0
Fe
-43.0
± 0.5
-706.35
-5.8(4.6)
Co
-47 ±
2
-772.0
-16(5)
Ru
-38.7
± 0.5
-656.1
-25(7)
aAll values taken from Table 1-2 (temperature = 350 K)
^Values given are negative of the third ionization potentials of the
metals taken from ref. 137. Conversion factor = 23.065 Real mol’1
= 1 eV
cElectron affinity data for atomic metals taken from ref. 138. Number
in parenthesis is the uncertainty in the last figure(s).

93
between AHhom°(M-0) and the average heterolytic metal oxygen bond
enthalpy, AHhet°(M-0), is given in eq 5-3.
AHh°et(M-0) -
6 AHhom (M-0)
¿iIP(M) + 3AHa°(acac-)
i-i
5-3
The summation term in eq 5-3 is the sum of the first three ionization
potentials for the metal M. Values for Ah^° for M(acac)3 complexes of
the first transition metal series are available in the literature from
the results of Wood and Jones using bomb calorimetry139 and from the
results of reaction calorimetry.140'143 Reaction calorimetry is
considered to be the more reliable method for M(acac)3 compounds,144,1413
and this technique has been applied to M(acac)3 complexes of interest
here for M = Cr, Mn, Fe and Co.141,142 Reaction calorimetry has been
used by Ribeiro Da Silva and co-workers to determine values of AHf° and
AHh0m0(M-O) for other tris J3-diketonate complexes, and the application of
the technique to transition metal J3-diketonates has been reviewed.141
Their work included a reappraisal of of the values of AHf° and
AHhom°(M-0) derived from the original reaction calorimetry studies, and
the values have been revised here using the latest values of the
auxiliary thermochemical data required for their determination.
The two values that introduce the greatest uncertainty in derived
bond enthalpies for the M(acac)3 complexes are the values of the gas-
phase homolytic bond dissociation enthalpy of the O-H bond in the enol
form of acetylacetone (AHhom°(H-acac) in eq 5-2) and the enthalpy of
sublimation of the M(acac)3 complex. Values for AHsub°[M(acac)3] are
difficult to measure precisely for compounds of relatively low
volatility such as M(acac)3 complexes. For example, values for AHS(jb°
for Cr(acac)3 quoted in the literature range from 6.64 kcal mol'1, used
in the bomb calorimetry study of Wood and Jones,139 to 33.8 kcal mol'1
obtained more recently from differential scanning calorimetry.145 The
apparent unreliability of the values of AHsub°[M(acac)3] used in the

94
earlier work was recognised in the reappraisal by Ribiero Da Silva and
co-workers.142 From a review of the results available in the
literature,143 the values of AHsub°[M(acac)3] chosen by these workers were
in the range of '28-33 kcal mol"1. The same values were used in this
report and are given in Table 5-2 along with the other auxiliary data
used in Figure 5-2.
No experimental values have been available for the value of
AHhom0(H-acac), and values used previously have been estimated. The
difficulty of assessing the contributions to the relative stability of
acetylacetone due to intramolecular hydrogen bonding in the enol form
and the effects of electronic delocalization in the acetylacetonate
radical has led to estimated values ranging from 87-110 kcal mol"1.139,144
A value of AHhom°(H-acac) can be obtained from the gas-phase proton
affinity (Ahra) of acac",146 AHg° of acac- and the ionization potential of
H atom.137 The relationship is given by eq 5-4.
AHhon,°(H“acac) = AHpA(acac") - IP(H(g)) - AHa°(acac) 5-4
Substituting the available data from the literature and AHg° for acac*
determined in this report (Table 5-2) into eq 5-4 yields a value of
AHhom°(H-acac) of 90 ± 5 kcal mol'1.
The new value for the AHhom°(H-acac) combined with the reaction
calorimetry data leads to new values of AHhom°(M-0) and AHhet°(M-0) for
the M(acac)j complexes of Cr, Mn, Fe and Co, and these values are given
in Table 5-3. Also given in Table 5-3 are the values of
AAHhet°[M-(acac)30/" ] , obtained from eq 5-1 (a) and the data in Table 5-1.
The resulting AHhet°(M-0) and AHhom°(M-0) values from eqs 5-1 (a) and 5-1
(b) for the M(acac)3" anions are listed in Table 5-3.
The results for the average M-O heterolytic bond energies obtained
in this report (Table 5-3) are shown graphically in Figure 5-3 (diamond
points). The heterolytic bond dissociation enthalpies for the M(III)

95
neutral complexes are approximately twice the values of those for the
M(II) anions. Interestingly, this approximate factor of 2 is also found
in comparing the heats of hydration of M3+ and M2+ ions122,147 as well as
the mean heterolytic bond dissociation enthalpies of the M(III)
metallocenium ions and M(II) metallocenes, [Cp2M]+(g) and Cp2M(g).133 On
the basis of these limited comparisons, the ratio of average heterolytic
bond energies for these types of M(III) and M(II) complexes seems to be
associated more with the formal oxidation states of the metal than with
the charges on the complexes or the natures of the ligands.
The results in Table 5-3 indicate that the mean homolytic bond
dissociation enthalpies for the metal(II) anions are in all cases higher
than the values for the metal(III) complexes. Thermochemically, this
result can be traced to the higher electron affinities of the neutral
complexes compared to the free metal atoms (Table 5-1). The trends in
homolytic bond energies for metal complexes will generally be less
intuitive than found for organic compounds because significant
electronic rearrangements can occur upon bond formation in the metal
complexes. As expected, heterolytic energies follow a far more
predictable trend when the metal oxidation state is varied.
Although it may be considered that the results in Table 5-3 for
the M-0 bond dissociation enthalpies of the neutral M(acac)3 complexes
are more reliable, also shown in Figure 5-3 are the results for the
complexes taken directly from the published bomb calorimetry study139
(upper plot, circle points), which included an estimated value for
Ti(acac)j. The corresponding values for the M(acac)3" anions derived
from them are also shown (lower plot, circle points). The new values of
AHhet0(M-0) (triangles, Figure 5-3) are lower than those derived from
bomb calorimetry results because of the lower value used for
AHhom0(H-acac) and a more highly exothermic value for AHa°(acac') (a
value of -34 kcal mol'1 was used previously). The calculated values
using the bomb calorimetry results139 provide an illustration of the

96
l_
O
E
o
(J
O
o>
Figure 5-3. Average heterolytic M-0 bond energies for M(acac)3
complexes and M(acac)3' ions. Upper plot (circles) are results from an
early report using bomb calorimetry. Upper plot (diamonds) are results
from this work. The lower plot shows the corresponding values for
M(acac)3' ions. The trends from each study follow the classical double
periodic variation with relative minima occuring for d° and d5 metal
ions (Sc and Fe upper, Mn lower).

97
Table 5-2. Auxiliary thermochemical data (kcal mol'1) for M(acac)3 complexes
and acetvlacetone.
Cr
Mn
Fe
Co
AHsub° tM Íacac) 31
29.4 ± 0.7a
28.7 ± 2.4a
32.3 ± 2.4a
28.2 ±
1.2b
AHsub°
94.79 ± 1.0C
67.09 ± 1.0C
99.50 ± 1.0C
101.5 ±
O
O
rH
AHf°( complex)
-374.0 ± 2.1a
-329.6 ± 0.9a
-314.2 ± 0.7a
-294.9 ±
0.9b
AlWH-acac)
AGa°(acac‘)
AHvap°
AHf°(Hacac, 1)
AHf°(H,g)
90 ± 5d
-59 ± 3d
9.99 ± 0.05e
-101.7 ± 0.3f
52.104 ± 0.003c
aTaken from ref. 141.
bTaken from ref. 142.
cTaken from ref. 148.
dFrom this work, see text.
eTaken from ref. 149.
fTaken from ref. 150.

98
Table 5-3. Average metal-oxygen bond energy data fkcal mol ^) for gas-phase
M(acac), complexes and Miacac',' anions.
M
AAHheto/- a
[M-(acac)3u/ ]a
AHhom°(M-°)
M(acac)3
AHhet°(M-0)
M(acac)3
AHhet0(M-0)
M(acac)j
JV":0-1
M(acac)3
V
651
“
Cr
694
46
+
3b
Mn
717
34
±
3b
Fe
663
37
+
3b
Co
725
34
+
3b
Ru
617
225
+
5C
109
±
8
47
+
3'
223
+
5C
103
±
8
>
44
217
±
5C
107
±
8
43
±
3'
230
±
5C
108
±
8
39
±
4'
aValue obtained from eg 5-3 and gas-phase electron attachment data given in
Table 5-1.
dalue obtained from reaction calorimetry data in refs. 141 and 142 corrected
for value of AHhom°(H-acac)(g)) (see text).
cValue obtained using AHa° of acac from this work.
determined from value of AHhom°(M-0) using eg 5-1 (b)

99
formation of a part of the classic double periodic variation.147® This
trend is generally observed for heterolytic bond energies for M+3 and M+2
complex ions of the first transition metal series. The relative minima
at Sc and Fe for the neutral complexes, joined by a dashed line,
correspond to the d° and d5 configurations for which the crystal field
stabilization energy is zero.122,147a An analogous rationale applies to
the trend observed for the M(acac)3" anions, where the d5 configuration
for M(acac)3‘ anions occurs for Mn and a minimum value is again
observed.
Relative Solvation Energies of M(acac)-,(q) and M( acac )(q)
The difference in AGsolv° values between a M(acac)3 complex and its
anion (AAGsolv°[M(acac)307" ] )* is defined by eq 5-5, and applies to the
reaction in eq 5-6.
AAGsolv°[M M(acac)3(soln) + M(acac)3*(g) -» M(acac)3(g) + M(acac)3'(soln) 5-6
Thermodynamic data for reversible electron attachment to electroactive
species in solution are normally given as standard electrode potentials
(E° values), measured relative to the standard hydrogen electrode (SHE).
For many species this data can be conveniently estimated from E1/2
values, measured against a reference electrode, by using, for example,
polarography or cyclic voltammetry. In order to be able to directly
compare E1/2 data obtained for M(acac)307‘ couples to the corresponding
*The term AAGgolv0 [M(acac)3®7'] is intended to represent the free energy
change occurinq in the redox couple M(acac)3°7' and not the quantity
AGsolv°[M(acac)3 1 ” AGsolv°[M(acac)3 "1 ' wh:*-ch “as the opposite sign.

100
gas-phase AGg° values, the zero of potential for the "free" electron in
reactions b and c of Figure 5-1 must be set to the same reference state.
Adopting the stationary electron convention, as done for gas-phase AGg°
values, defining "absolute" magnitudes of electron attachment energies
in solution requires that the potential of the reference electrode be
redefined on this absolute scale (to yield an Eabg°(ref) value). The
absolute electron attachment energy for M(acac)3 complexes in solution
(AGa°[M(acac)3(soln)] is then estimated by eq 5-7, where F is the
Faraday constant.
AGa°[M(acac)3)(soln)] = F {E1/2[M(acac)30/'] + Eabs°(ref)} 5-7
With a value for AGa°[M(acac)3) (soln) ], a value for AAGsolv°[M(acac)30/‘]
can be obtained from eq 5-8, as illustrated by cycle II in Figure 5-1.
AAGsotv°[M30/'} = AGa°[M(acac)3) (soln) ] - AGa°[M(acac)3) (g) ] 5-8
The absolute value of the electrochemical potential of a galvanic
half-cell is thermodynamically related to single ion solvation energies.
Although relative single ion solvation energies are readily obtainable
from Born cycles and emf measurements, the absolute contribution from
each ion to the solvation energy of ± ion pairs is difficult to
evaluate. There have been attempts to estimate the absolute value of
the enthalpy and free energy of hydration of the proton. 151-155,94-98 A
variety of different methods have been used, which have been categorized
into three groups by Haliwell and Nyburg,153 and the various methods
that have led to literature values for the thermodynamics of H+
solvation have been critically reviewed by Conway.156 A recent value
for the free energy of hydration of the proton of -260.0 ± 0.5 kcal
mol’1 has been provided by Farrell and McTigue,96 based on measurements
of volta potential differences. This method has the advantage that it

101
provides the most direct method for the determination of "real" free
energies of solvation of ions, and intrinsically includes the work
required to pass a charge across the surface potential (Ax) that exists
at the surface of liquids. This work is not included in the values of
AHsolv° or AGsolv° obtained by applying "physical model" approaches,153,156
and such values are termed "chemical" free energies of hydration. A
drawback of the volta potential method is that the reference state of
the electron is stationary at a point in a vacuum close to the surface
of the solution, under the influence of the volta potential of the
solution (Ys). As shown by Trasatti,157 an amount of work equal to zFYs
must be done to move the electron away to field free space (the
reference state used to define single ion solvation energies in accord
with the stationary electron convention). The magnitude of this work is
uncertain. As no experimental procedure has directly led to the single
ion solvation free energy of the proton with the necessary free electron
reference state, one is left with choosing a value based on a method for
which the assumptions and principles are the least unsatisfactory.
The value of AGhyd° (H+) quoted by Farrell and McTigue is in good
go
agreement with an earlier determination by the same method by Randles,
and is not dissimilar to estimated values based on physical models.
154 This value has been used by Heinis and co-workers14 and by Shalev
and Evans20 in a cycle similar to II in Figure 5-1 to determine the
solvation energies of a variety of quiñones and nitrobenzenes. Adopting
the recommended value156 for AGhyd° (H+) allows the absolute potential of
the standard hydrogen electrode to be evaluated,94'98,155,157 and a value
of -102.6 kcal mol'1 (4.44 eV) is obtained as the absolute potential for
the SHE. Values for Eabs°(ref) based on this scale are used with E^2
data in eqs 5-7 and 5-8 to obtain values for AGa°[M(acac)3) (soln) ] and
AAGsolv°[M30/']-

102
Table 5-4. Polaroqraphic Data and Solvation Free Energies of M(acac),^
complexes in various solvents.
M(acac)30/"
Couple
e1/23 AGa°[M(acac)3(soln) ]b AAGsolv°[M(acac)30/']b
Acetonitrile
Cr
-1.81c
-66.3
-46
Ru
-0.70d
-91.3
-52
Fe
-0.67c
-92.6
-50
Co
-0.34e
-100.0
-53
Mn
-0.09f
-110.6
-52
Dimethylsulfoxide
V
-1.429
-75.2
-50
Dichloromethane
Ru
-0.71d
-91.1
-52
Water
Ru
-0.51h
-96.2
-58
(-75')
aValues given in volts measured using 0.1 M TEAP as supporting
electrolyte against SCE, except d, n-BuNBF, Vs Ag/AgCl and h, see ref
158.
Valúes given in kcal mol'1, obtained from egs 5-9 and 5-10.
cTaken from ref. 159.
dTaken from ref. 160
eTaken from ref. 161.
*Taken from ref. 162
sTaken from ref. 163.
hTaken from ref. 158.
'Value of single ion solvation free energy in water.

103
Polarographic data are given in Table 5-4 for the reversible
electrochemical reduction of several M(acac)3 complexes in acetonitrile
cited from various literature sources. To facilitate comparison, data
are quoted wherever possible from results obtained under common
electrochemical conditions (acetonitrile with 0.1 M tetraethylammonium
perchlorate as supporting electrolyte). For V(acac)3, however, E1/2 data
is only available for DMSO as the solvent. To allow a comparison of
solvation free energies in different solvents, data for the reduction of
Ru(acac)3 in dichloromethane and water are included. The E1/2 data lead
to values of AGg0[ (M(acac)3) (soln) ) and AAGsoiv°[M(acac)30/‘], which are
also included in Table 5-4. The accuracies of these values are
difficult to assess since they rely on the value chosen for the single
ion solvation energy of the proton and the approximation of E1/2 to true
E° values. Unfortunately, due to the low solubility of M(acac)3
complexes in water, the latter approximation is made worse for the
majority of the data in Table 5-4, since the E1/2 values quoted are
measured in non-aqueous solvents against an aqueous reference electrode.
Consequently any junction potential that exists at the solvent/reference
electrode interface will be included in the observed E1/2 values. This
problem was minimized by Shalev and Evans20 in obtaining AAGsolv° values
for organic compounds by including a cobaltocenium/cobaltocene internal
standard. The absolute standard potential of this Cp2Co couple was
assumed to be largely solvent independent as is assumed for the Cp2Fe+/0
couple, but this assumption is known to be somewhat unsatisfactory
because of different solvent ordering effects for various polar
solvents.16^ The value of AAGsolv°[Ru (acac)3] obtained in water, however,
may be considered to be a reasonable estimate since junction potentials
are minimized and E^2 will closely approximate E°.
Figure 5-4 shows a plot of gas-phase AGa°[M(acac)3(g)] values
versus AGa°[M(acac)3(soln)] values in acetonitrile for the M(acac)3
complexes for which data are available (Tables 5-1 and 5-4). The value

104
Figure 5-4. Plot of electron attachment energies for M(acac)j complexes
in the gas-phase versus the estimated values in acetonitrile. The
electron attachment energy for V(acac)3 in the gas-phase versus in DMSO
is also shown.

105
V Cr Mn Fe Co
Figure 5-5. Plot showing periodic trends of electron attachment
energies in the gas-phase and in solution. Solution-phase data are for
acetonitrile (circles) and DMSO (star).

106
for V(acac)3 is also shown since E1/2 values for M(acac)3 complexes in
DMSO are typically similar to those in acetonitrile, generally being
some < 100 mV or so more positive. As can be seen, there is a strong
linear correlation between the two data sets. The slope of the best fit
line is close to unity (1.1), indicating that differential solvation
energies for M(acac)30^" couples are essentially constant (Table 5-4).
It should be noted that this conclusion is independent of the choice of
the absolute electrode potential. The same data is presented in Figure
5-5 as a periodic trend to illustrate the relative magnitudes of
electron attachment energies in the gas-phase and in solution.
It is interesting to compare the experimental values of
AAGsolv°[M(acac)30/‘] in Table 5-4 to the values predicted from dielectric
continuum theory. The Born equation12** predicts the change in
electrostatic free energy AGel° when a charge is transferred from a
conducting sphere of effective (thermochemical) radius re^ in a vacuum,
to a sphere of equal radius in a medium of dielectric constant D. A
convenient form of the equation for ions in solution is given in eq 5-9.
AGel° = - (166zz/reff) (1 - 1/D) kcal mol'1 5-9
In eq 5-9, z is the integral units of electronic charge and D is the
dielectric constant of the solvent. It can be seen from the above
definition that the Born equation applies to the process in eq 5-6, and
therefore AGel° can be related directly to AAGgoiv°. The Born equation
includes "chemical" single ion free energies of solvation, since the
work of transferring an ion across the surface of the solvent is not
considered. The additional work is probably small however, when
compared with typical values of AAGgolv0,157 and so useful comparisons may
still be made to the AAGgolv°[M(acac)30/'] obtained in this work.
Using the value of AAGsolv°[Ru(acac)30/‘] of 57.5 kcal mol"1 in
water, the Born equation gives a value of reff of 2.9 Á, while the

107
maximum radius for Ru(acac)30/' is expected to be ' 6 k, the maximum
radius of Ru(acac)3.^5 The smaller Born thermochemical radius, compared
to the crystallographic radius, is not unexpected since the molecular
shapes and charge distributions in the M(acac)30/’ couple are poorly
approximated by neutral and charged spheres. The tris chelate
coordination environment can allow the first solvation layer to
penetrate the "6 k sphere based on the distance between metal center and
methyl hydrogens. The relative extents to which solvent penetration and
specific solvation of the polar metal-ligand interactions influence the
solvation energies cannot be deduced from the present results. It is
notable that the deduced AAGsolv°[Ru(acac)30/'] values for dichloromethane
and acetonitrile solvents are 6 kcal mol'1 lower than the value for
water. Given the approximations inherent in the method used, however,
this magnitude of difference could arise from either actual variations
in solvation free energies for the nonagueous vs. water solvents or
errors introduced by the electrochemical potential determinations.
Single ion solvation free energies for M(acac)3' ions can be
obtained from AAG^^tMiacac)^’ ] values, provided that the solvation
energy for the gas-phase neutral is known (eq 5-7). The solvation free
energy for the neutral can be obtained from the relationship
AGsolv°[M3 the term AGsoln°[M(acac)3(c) ] is the free energy of solution of
crystalline M(acac)3. Values of AG$ub° are not available from the
literature, but estimates can be obtained from AHsub°[M(acac)3(c)] by
assuming that ASsub°[M(acac)3(c) ] is equal to the translational entropy
of the vapor produced. Translational entropies can be predicted quite
accurately from the Sackur-Tetrode equation (see chapter 3). For
compounds such as M(acac)3 complexes, for which the crystal lattice is
held by essentially Van der Vaals forces, estimated values of AGS(jb° are
expected to be quite reliable (for example, the experimental value of
Assub° ^or naPhthalene is 40.3 cal mol"1 K'1 while the Sackur-Tetrode

108
equation predicts Astrang° for naphthalene to be 40.5 cal mol"1 K"1).
Considering the Ru(acac)3 couple, from an estimated value of AHgub° of
34 ± 3 kcal mol'1, based on the values for other M(acac)3 complexes,
together with an estimated value of ASgub°[Ru(acac)3(c) ] of 43.8 cal
mol’1 K'1, a value of AGS(jb° of 21 ± 3 kcal mol"1 is obtained. A value of
^Gsoln° 3.1 kcal mol"1 for Ru(acac)3(c) in water can be calculated from
its solubilty,158 which gives AGgolv° of Ru(acac)3(g) in water of -17.7 ±
3 kcal mol"1. Combining these data with AAGgolv°[Ru (acac)30/" ] in water
(Table 5-4) gives AGg0^v°[Ru (acac)3" (g) ] of -75 ± 10 kcal mol"1.
The vertical ionization energies of several ruthenium tris(fl-
diketonates) have been combined with polarographic data by other workers
to obtain information about relative solvation energies.165 For these
Ru compounds, the ionization is from a metal-based approximately non¬
bonding orbital, and the PES data may be jusifiably used in place of the
adiabatic values with relatively small errors.
Relative Solvation Energies of RuftfacUfg) and RufhfacWfq)
and Their Negative Ions
Many ruthenium tris(fi-diketonates) are stable with respect to
reversible one electron electrochemical reduction and E1/2 values for
these complexes have been reported for a variety of 8-diketonate ligands
by using cyclic voltammetry.72'76 The estimates obtained in the present
work for gas-phase AGa° values for the complexes Ru(hfac)3, Ru(tfac)3 and
Ru(acac)3 can be combined with the appropriate electrochemical data to
yield values of AAGgotv° for the redox couples Ru(tfac)3°7’ and
Ru(hfac)30/", and AGg°[Ru (tf ac) 3 ( soln) ] and AGa°[ Ru (hf ac )3 ( soln) ] , as was
done above for Ru(acac)3 and the other M(acac)3 complexes. Data for E1/2
values in acetonitrile are available for these complexes and so the
values obtained may be compared to the related data in Table 5-4. For
Ru(tfac)3, values of 38 kcal mol'1 for AAGsolv0[Ru(tfac)07'] and 102 kcal
J

109
mol"1 for AGa°[Ru(tfac)3(soln)] are obtained. For Ru(hfac)3 values of 30
kcal mol"1 for AAGsolv°[Ru(hfac)0/" ] and 119 kcal mol"1
AGa°[Ru(hfac)3(soIn)] are obtained. The values of AAGsolv° steadily
decrease for the series Ru(acac)3, Ru(tfac)3, Ru(hfac)3 as the degree of
fluorination of the ligand increases. The AGa°(soln) versus AGg°(g) data
for the three complexes are plotted in Figure 5-6 in the same way as was
done for the M(acac)3 complexes in Figure 5-4. The slope of the line is
0.55 for the series of ruthenium complexes, which can be compared to the
value of 1.1 for the series of M(acac)3 complexes. The smaller value
reflects the decreasing solvation energy of the Ru(fi-diketonate)3 anions
with increasing fluorination.
This result is analogous to the observation made for a series of
substituted benzo-, naptho- and anthraguinones that the greater the
electron attachment energy, the smaller the corresponding increase in
the E1/2° value.14,15 It was noted that the compounds with greater
electron attachment energies are those more able to delocalize the
negative charge. By the same argument however, this leads to a
correspondingly lower solvation energy, as predicted by dielectric
continuum models.124 A plot of E1/2 versus AGa°(g) values for the organic
acceptors led to curvature in the slope line at higher energies with the
slope of the line becoming less than unity.
An analogous rationale can be applied to the difference in the
slope of the AGa°(soln) versus AGa°(g) values for the M(acac)3 and Ru(B-
diketonate)3 complexes. For the M(acac)3‘ ions the distribution of
negative charge is probably affected little by the nature of the metal,
which accounts for the relatively constant value of AAGso1v° obtained for
the series of M(acac)30/" redox couples. For the series of Ru tris(B-
diketonate) complexes the negative inductive effect (-1) of the fluorine
atoms will serve to delocalize the negative charge. The resultant
effect is that the gas-phase electron attachment energies increase with

AGa°(Ru(/3—diketonate)3(soln))
(kcal mol-1)
no
—AGa°(Ru(/S—diketonate)3(g))
(kcal mol-1)
Figure 5-6. Plot of electron attachment energies for Ru(J3-diketonate)j
complexes in the gas-phase versus solution (acetonitrile).

Ill
ions decrease. Since the values of f°r t*le couP^es become more
increasing fluorination, while the solvation energies of the negative
positive in value (more strongly oxidizing) with increasing
fluorination, the increase in gas-phase electron attachment energy is
greater than the loss of solvation energy in the redox couples, and this
results in the slope of the line in Figure 5-6 of less than unity.
Conclusions
The availability of free energies of electron attachment for a
series of gas-phase metal tris acetylacetonate complexes has allowed the
first systematic thermochemical evaluation of average bond dissociation
enthalpies as a function of metal and oxidation state in gas-phase
coordination complex ions. The thermal electron-transfer gas-phase
equilibrium method yields free energies of electron attachment (or
ionization) that can be directly incorporated into thermochemical
cycles. Other methods of determining such energies, such as
photoelectron spectroscopy, are less generally useful since transition
metal complexes often undergo large geometry changes upon oxidation or
reduction that can lead to erroneous estimates of thermal electron
attachment or ionization energies. In addition, when combined with
solution electrochemical data, the AGg° values for the gas-phase neutral
complexes have led to the most extensive evaluation to date of
differential solvation energies, AAGsolv°, for transition metal complex
redox couples. In contrast to the results for the
metallocene/metallocenium couples reported elsewhere,133 the Born
charging model does not provide a reasonable estimate of the
differential solvation free energy for the tris chelate complexes
studied here. Although the inadequacy of the Born model combined with
crystallographic radii for predicting solvation free energy changes for
redox processes for many transition metal complexes has been suggested

112
in other contexts (e.g., in attempted fits of optical electron-transfer
phenomena using the dielectric continuum model166), direct
thermochemical evaluation of these effects has been lacking until this
study. Finally, the AAGsoly0 values can be used to derive single ion
solvation free energies for complex ions if the free energy of solvation
for the neutral complex is available.
In considering the data in Tables 5-1, 5-3 and 5-4 it is striking
to note how greatly the the range and magnitude of the electron
attachment energies for the free M3+(g) ions (29.3 - 33.7 eV) are
diminished in corresponding the M(acac)3 complexes (0.9 - 2.6 eV).
Solvation of a gas-phase M(acac)3 complex increases the electron
attachment energy by a relatively constant amount (“2.2 V for
acetonitrile as the solvent). The role of solvation is therefore
somewhat secondary to that of ligation (cycle I in Figure 5-1) in
determining the magnitude of the electrode potential for a particular
M(acac)j0/" redox couple. However, when considered on the scale of
typical free energy changes for homogeneous redox reactions of
transition metal complexes, changes in solvation energies in reactants
and products clearly can have a profound influence on the reaction
thermodynamics. As more gas-phase data become available, a more
complete quantitative understanding of solvation and bond energies in
coordination chemistry will certainly result.

CHAPTER 6
INTERPRETATION OF THE TRENDS IN THE ELECTRON ATTACHMENT
FREE ENERGIES OF THE TRIS(ACETYLACETONATE) AND
TRIS(HEXAFLUOROACETYLACETONATE) COMPLEXES OF THE
METALS Ti-Co USING THE SIMPLE LIGAND FIELD MODEL
Introduction
Previous accounts in the literature that compare periodic trends
in electron attachment energies for series of transition metal ions in a
given coordination environment have been restricted to studies of trends
in electrochemical reduction potentials (E° or E1/2 values), since gas-
phase electron attachment energy data were not then available. In these
early reports, ligand field theory was used to explain the observed
trends in electrochemical reduction potentials. One of the most well
known and continuous series of redox couples is the M(H20)63+72+(aq)
series, where M represents a first row transition metal, and trends in
redox potentials for this series have perhaps received the most
attention in the literature. A close correlation has been demonstrated
between the trends in the third ionization potential of the series of
M(g) ions and the oxidation potentials for the series of M(H20 ) 63+/2+(aq)
couples, after "correction" for ligand field effects in the
complexes.35"37 The difference in absolute magnitudes has also been
quite accurately accounted for by the use of thermochemical cycles that
involve the heterolytic metal-ligand bond energies in the oxidized and
reduced complexes, solvation energies, and an estimate of the absolute
potential of the standard hydrogen electrode. These relationships were
discussed for M(acac)3 complexes in chapter 5.
A more complete understanding of the electronic effects that
determine the magnitudes and trends of electron attachment energies for
113

114
metal complexes could be gained from detailed molecular orbital
calculations, performed on both the oxidized and reduced forms of a
series of complexes. However, the crystal field model, which has
previously been used to explain trends in electrochemical reduction
potentials, is applied here to the trends in gas-phase AGa° values for
the M(acac)3 complexes.
Thermochemical Relationships and Periodic Trends
The amount of energy released when an electron reversibly binds to
a ligated metal ion is dependent on the metal ion and its oxidation
state, the change in the total metal-ligand bond energy, and for
electron attachment in solution, the change in solvation energy. For
complexes with metal-based redox orbitals, the relationship between the
thermodynamic quantities involved is illustrated by the energy cycle in
Figure 5-1. Electron attachment energies for gas-phase metal complexes
obtained from the charge-transfer equilibrium technique described in
this dissertation are free energies. For complexes in solution, data
obtained from polarography using the relationships described in
chapter 5 are also free energies. For X = G (free energy) in Figure
5-1, the difference in electron attachment free energy between a free
ion and a gas-phase complexed ion is given by eq 6-1, and that between a
free ion and a complexed ion in solution by eq 6-2.
AGa°[MLYn(g) ] - AGa°[Mz(g)]= AAGhet°[ (M-LY)n/(n'1) ] 6-1
AGa°(MLYn(soln) ] - AGa°[Mn(g)]= AAGhet°[ (M-LY)n/<"-1> ] - AAGsolv°[ (M-Ly ) n/(n'1 > ]
6-2
In eqs 6-1 and 6-2 the term AAGhet°[ (M-Ly)n/(n'1)) is the difference
between the total heterolytic metal-ligand bond free energies in the

115
oxidized and reduced complex and AAGsol y°[ (M-Ly)n/(n'15 ] is the difference
between the free energies of solvation for the oxidized and the reduced
complex. Substituting MLyn(g) = M(acac)3 for the complexes studied in
the present work into eq 6-1, and separating free energy terms into
enthalpic and entropic contributions, eq 6-1 leads to eq 6-3.
AGa°[M(acac)3(g) ] - AHa°[M+3(g) ] = AAHhet°[M(acac)3(g) ]
- T(ASa°[M(acac)3(g) ]) 6-3
Electron attachment energies for free metal ions are given by the
negative value of the third ionization potential (IP3) of the metal, and
apply to a temperature of absolute zero. Throughout this dissertation,
the stationary electron convention is adopted for dealing with the
thermochemistry of electron attachment to gas-phase species. This
convention, applied to free energies of electron attachment, was
discussed in chapter 3. Under the stationary electron convention the
electron has no heat capacity or entropy, and therefore IP3 and
-AHa°[MLyn(g)] are equivalent at all temperatures.
Since the AGa°[M(acac)3(g) ] values obtained in the present work
are for the metals Ti-Co, from eq 6-3 and Figure 5-1 they can be related
to the values of AHa°[Mz(g)] for the corresponding free ions (Ti+3-Co+3).
Values of -AHa°[M3+(g)] for the metals Ti-Co in Table 5-1 are plotted in
Figure 6-1 (a). The origins of the characteristic trend line are well
established and have been semi-quantitatively discussed by Griffith167
using the Slater-Condon-Shortly model of the electronic structure of
free atoms and ions. In Figure 6-1 (a), the overall increase in
-AHg0[M+3(g)] values with increasing atomic number of the metal is
attributed to the increase in nuclear charge. The variance within the
upward trend is a result of differences in e-/e- exchange and repulsion
energies operating in each M2+/M3+ couple. The abrupt decrease in

116
Figure 6-1. Plot of trends in electron attachment energies. Upper plot
(line a) shows the electron attachment energies for free M+3(g) ions.
Lower plot (line b) shows the electron attachment free energies for the
M(acac), complexes, and the values corrected for liganf field effects
(line c).

117
-AHa(M+3(g)] from Mn3+ to Fe3+ provides a good illustration of these
effects. Forming Mn2+ (d5) from Mn3+ (d^*) results in the single largest
increase in the number of stabilizing electron exchange interactions.
The enhanced stability of the d5 configuration is commonly referred to
as the "special stability of the half-filled shell." On forming Fe2+
(d6) from Fe3+ (d3) the added electron enters a singly occupied orbital
with spin antiparallel to the five electrons already present. The
effect of the electron repulsion cannot be stabilized by exchange
interactions (since there are no other d electrons of the same spin),
and the result is that -AHg is approximately 70 kcal mol'1 less
energetic for Fe3+ than for Mn3+, despite the greater nuclear charge of
Fe3+.
Figure 6-1 (b) shows a plot of the values of AGa°[M(acac)3(g)]
obtained in the present work, which are given in Table 1-1. On
comparison to the plot of AHa°[M+3(g)] values in Figure 6-1 (a), the most
striking difference is that the values of AGa°[M(acac)3(g)] are in the
range of 30 eV less exothermic than the values of AHa°[M+3(g)]. Also,
although the increasing trend in -AHa°(M+3(g)] values from on going from
left-to-right is also discerned in the trend for the complexes, the
range in values is reduced from ~7 eV to ~2eV, coupled with some
prominent differences between the two trend lines.
From the right-hand side of eq 6-3, the difference between
electron attachment energies for AHa°[M+3(g)] and AGa°[M(acac)3(g)] can
be attributed to the terms AAHhet°[M(acac)30/" ] and TASa°[M(acac)3(g) ] .
The entropy change accompanying electron attachment to M(acac)3
complexes was discussed in chapter 4, where some evidence was presented
that suggests that ASa°[M(acac)3(g) ] is probably between 2-20 cal mol'1
K . Hence, as dicussed in chapter 5, the experimental values of
-AGa°[M(acac)3(g)] at "350 K, obtained in the present work, are expected
to be a few kcal mol'1 greater than for -AHa°[M(acac)3(g) ]. This
difference is small compared to the values of AAHhet°[M(acac)30/'] (“700

118
kcal mol'1 see Table 5-3), and so the value of AAHhet°(M(acac)30/'] are
the principle cause of the large difference in electron attachment
energies between the free ions and the complexes. Further, the
irregularity in the periodic variance of AAHhet°[M(acac)30^’] values can
be identified as the major cause of the prominent differences between
the periodic variance of AGa°[M(acac)3(g) ] and AHa°[M+3(g)] values.
Trends in heterolytic M-L bond energies involving transition metal
M3+ and M2+ ions, display a characteristic double periodic variance over
the electronic configurations d°-d10 at the metal center. For example,
Figure 6-2 shows the trends in the enthalpies of hydration (AHhyd°) for
the series of ions Sc3+ - Ga3+ and Ca2+ - Zn2+, which span the electronic
configurations d° - d10. Values for Sc2+, Ni3+, Cu3+ and Zn3+ are unknown.
For both series, a relatively straight line can be drawn through the
points for the d°, d5 and d10 ions. A simple interpretation of the
deviations from a linear increase in AH^0 is provided by the crystal
field model.
The crystal field model. In the crystal field model, the energies
of the degenerate d orbitals in a free transition metal ion are
considered in terms of the perturbing effect of points of negative
electrostatic charge located at the same spatial positions occupied by
ligand donor atoms in complex metal ions. For octahedral ML6 complexes,
the six point charges lie equidistant from the metal ion along the three
cartesian axes. The electrostatic field generated by the six point
charges can be resolved into spherical and octahedral components. As
the point charges are positioned nearer to the metal, the spherical
component of the electrostatic field raises the energy of all the d
orbitals due to a repulsive effect with the negatively charged
electrons. The effect of the octahedral component splits the energy of
the five degenerate d orbitals into two sets. The orbitals of eg
symmetry lie along the cartesian axes and interact more strongly with

(kcal mo
119
1150-3
1100-E
1 050 i
1000Í
950
900 ^
■>° Ga+3
/
O
"O
0 1 2345678910
dn Configuration
Figure 6-2. Plot of the enthalpies of hydration of the first transition
metal series M+^ and M+^ ions, (a) M+ ions; (b) M+ ions.

120
POTENTIAL
ENERGY
M(acac) 3
Complex
"Corrected"
4EfcM(acac)3
M*2
Electron
attachment
energy of
free ion
Free Ion
Figure 6-3. Effect of an octahedral ligand field on the energies of the
d orbitals of M+3 and M+2 ions.

121
the point charges than the orbitals of t2g symmetry which are directed
between the axes. Therefore, the eg set lie at higher energy relative
to the t2g set. These effects are illustrated for M+2 and M+3 ions in
Figure 6-3. The ligand-field parameter that expresses the magnitude of
the splitting in energy of the d orbitals is Dg. The t2g orbitals lie
at an energy of 4Dq lower than the energy barycenter resulting from the
spherical component of the electrostatic field, and the eg set lie 6Dq
higher (Figure 6-3). The energy difference between the two sets of
orbitals is therefore lODq. Note that the energy of the d orbitals for
the M+3 ion are raised in energy to a greater degree than for the M+2
ion. In the crystal field model this is caused by the stronger
attraction of the negative point charges to the +3 charge than the +2
charge and is the interpretation of the greater metal-ligand bond
strength in the M(acac)3 complexes than M(acac)3'. Values of lODq can
be obtained quite conveniently from absorbance spectra, usually in the
visible region. This can be done graphically, by using term diagrams.
The measured spectrum is fitted as closely as possible to the diagram
and the Dq or Dq/B value is read from the abscissa. In some cases (d3,
d6, and d8) the maximum of the first spin-allowed band yields the value
of lODq directly. In other cases (d2, d6 (low spin) and d7) lODq cannot
be obtained directly and configuration or term interaction must be
considered.
In the crystal field model, for any high-spin d-electron
configuration subject to the same octahedral ligand field, the energies
of the configurations d°, d5 and d10 are unaffected by the value of lODq,
since the stabilizing effect of occupying the t2g orbital set is offset
by an equivalent loss of energy by occupying the eg set. All other
ground state configurations are stabilized relative to the hypothetical
case where the d orbitals are degenerate in the complexes, due to
predominant occupancy of the lower energy t2g set. The lowering in
energy is termed the ligand field stabilization energy (LFSE). For

122
typical values of lODq, LFSE can be significant and gives rise to the
characteristic double periodic trend observed in Figure 6-2. For
example, Dg for the complex Cr(H20 ) 63+, which has a d3 configuration, is
1770 cm 1. The three d electrons all occupy the t2g orbital set and LFSE
is 12Dq = "60.7 kcal mol*^
An important question concerns the type of thermodynamic state
function that should be compared to spectroscopic energy parameters.
Since state energies are obtained from Franck-Condon transitions, it
would appear that in the absence of pressure-volume work the relevant
thermodynamic quantity derived spectroscopically would be enthalpies.
However, values of lODq are temperature dependent since they derive from
band maxima, which are temperature dependent as a result of changes in
the population of ground state vibrational levels with temperature and
structural changes that may occur as the temperature changes. Thus, the
"proper" thermodynamic quantity to be identified with spectroscopic
parameters is not rigorously defined (unless the experiments are all at
0 K, where TAS is zero).
Correlating trends in AG^°rM(acac)3(g)l and AH^fM^an using
spectroscopic LFSE values. It is convenient to separate the the
difference in heterolytic bond enthalpies for the M(acac)3 and M(acac)3’
complexes into two components according to eq 6-4.168
AAHhet°[M(acac)30/‘] = AAHhet,o[M(acac)30/'] + ALFSE 6-4
In eq 6-4 the term AAHhetl°[M(acac)30/* ] is the difference in heterolytic
bond enthalpy that would arise from the purely spherical component of
the ligand field in the crystal field model, and includes electrostatic,
covalent, polarization and steric effects not present in ALFSE.
Combining equations 6-3 and 6-4 gives equation 6-5.

123
AGa°[M(acac)3(g) ] - ALFSE = AHa°[M3+(g) ] + AAHhet,o[M(acac)30/-]
- T(ASa°[M(acac)3(g)]) 6-5
Since the periodic variance of AAHhet,°[M(acac)30/" ] can be expected to be
essentially smooth, and the effects of T(ASa°[M(acac)3(g) ]) are
relatively minor, from eq 6-5 a plot of AGg°[M(acac)3(g) ] - ALFSE can be
expected to reproduce the trend line generated by the values of
AHa°[M3+(g)] in Figure 6-1 (a). However, in order to calculate ALFSE it
is necessary to obtain values of Dq for both the M(acac)3 complexes and
the M(acac)3' ions.
There have been several reports in the literature on the ligand
field parameters for M(acac)3 complexes, determined from analyses of
visible spectra. 169,170 Unfortunately, the presence of intense charge
transfer bands partly obscure the d-d transitions, making it difficult
to obtain reliable values. However, Jorgensen f parameters can be
derived for fi-diketonate ligands, and values of lODq of sufficient
accuracy may be obtained for M(acac)3 and M(acac)3’ complexes, when
combined with established g parameters for the M(III) and M(II) ions
respectively. Values of f for a series of tris(B-diketonate) chromium
complexes have been determined by determining the absorbance maximum of
the 4A2g -* 4T2g transition for each complex in a solution of
chloroform100. The energy of this transition gives a value of lODq
directly. Values of f for Cr(acac)3 and Cr(hfac)3 were calculated to be
1.05 and 1.03 respectively, and were found to be almost identical for
all the other complexes studied. To determine whether these f values
are applicable to gas-phase complexes, the absorbance maximum of the
^A2g -» ^T2g transition was measured for Cr(hfac)3, in the gas-phase at
-350K, and in ethanol solution. The results are presented in Figure
6-4.

124
Figure 6-4. Comparison of the band maxima for the %» "VS transition
in Cr(hfac)^. Line a is the absorbance of Cr(hfac)3 in the gas-phase
and line b is the absorbance in solution (ethanol).

125
It can be seen that the absorbance maxima occur at approximately the
same wavelength, suggesting that the effect of the solvent has
apparently little affect on the relative energies of the electronic
states in fi-diketonate complexes.
The difference in electron attachment energy between the complexes
and the free ions that results from differences in e-/e- interactions
are ignored in the simple ALFSE approach. The method is therefore only
directly applicable to high-spin complexes, since the multiplicities of
the ground states for the complex and the free ion are the same.
However, the nephelauxetic effect of the ligands will reduce electron-
electron repulsion effects in the complex. The success of the simple
field approach in successfully accounting for the trends in electron
attachment energies for series of transition metal complexes relies,
therefore, on this effect being small compared to the changes in
heterolytic bond energies for the complexes.171 For low spin complexes,
large pairing energies must also be included in the the value of ALFSE.
This additional correction must be included in the value of ALFSE for
the Co(acac)307' couple, since Co(acac)3 has a low-spin d^ configuration.
From the appropriate ligand field expressions, Tanabe and Sugano172 have
shown this energy to be equal to 5B + 8C, where B and C are the Racah
electron repulsion parameters for the metal complex. Values of Dq and
ALSFE for the gas-phase M(acac)307' couples are given in Table 6-1. The
value of ALFSE for the Co(acac)30/‘ includes the value of 5B + 8C
required to correct for the pairing energy in low-spin d6 Co(acac)3.
Values of the Racah parameters B and C for Co(acac)3 have been
determined by Tsiamis and co-workers to be B = 425 cm'1 and C = 3650 cm'
1.1^1 The value of ALFSE for the Co(acac)3 couple is given by -
8Dq(Co(II)) - (-24Dq(Co(III))) - (5B + 8C) = 1.1 eV (Table 6-1). In
Figure 6-1 (b), line c, the trend line is shown that results from
subtracting the appropriate values of ALFSE from the experimental
AGa°[M(acac)3(g)] values. As can be seen, there is a striking

126
Table 6-1. Ligand Field Parameters for M(acacK0/~ Complexes.
M g 10^ 'em’''3 ALSFE/eVb
V(II)
12.3
12.9
V(III)
18.6
19.5
Cr(II)
14.1
14.8
Cr(III)
17.0
17.9
Mn(II)
8.5
8.9
Mn(III)
21
22.1
Fe(II)
10.0
10.5
Fe(III)
14.0
14.7
Co(II)
9.3
9.8
Co(III)
19.0
19.8
0.01
1.56
1.64
-0.52
1.10°
aA = f.g, with f(acac) = 1.05.
hoifference in ligand field stabilization energies (strond field limit)
for the process M(acac), -» M(acac),’. A negative value implies that the
electron attachment is favored by XFSE.
cIncludes pairing energy 5B + 8C (see text).
resemblence to the trend line for the AHa°[M+3(g)] values, suggesting
that the simple crystal field model is adequate to explain the
divergence of the features of the trend lines for the AHa°[M+3(g)] and
AGa°[M(acac)3(g)) values.
Trends in AGa° values for M(hfac)3 complexes. The order of the
metals (M) in the series of M(hfac)3 complexes for increasing values of
AGa°[M(hfac)3(g)] have been determined in this work to be the same as
that for the series of M(acac)3 complexes. Since -AGa° for V(hfac)3 was
found to be approximately 50 kcal mol'1 greater than for V(acac)3, it
has been assumed that -AGg0 for all other M(hfac)3 complexes are also
"50 kcal mol"1 than the M(acac)3 complexes of the same metal. The

127
values of ASg° for M(acac)3 complexes can be expected to be similar to
the values for the corresponding M(hfac)3 complexes, and so from eq 6-3
the higher -AGa° values for the M(hfac)3 complexes must result from
AAHhet°[M(acac)3] being greater than AAHhet°[M(hfac)3] by *50 kcal mol'1.
In the M(hfac)3 complexes, the 18 fluorine atoms exert a strong
negative inductive (-1) effect. As a result, the electron density in
the highest occupied molecular orbital (HOMO) of a M(hfac)3‘ complex
will be more delocalized and contain more ligand character than the
corresponding HOMO of a M(acac)3‘ complex. The lower e'/e’ repulsion in
the M(hfac)3 complexes causes the smaller change in metal-ligand bond
energies and the greater electron attachment energies.
Correlating trends in E° for M(H..0) (ao) couples and
AH3°rM'f3ía^ 1. It is interesting to compare the above treatment for the
gas-phase electron attachment energies for the M(acac)3 complexes to
that used by previous workers to correlate the trend in the values of
the standard reduction potentials for M(H20 ) 63+/2+(aq) couples to the
trend in AHg0[M+3(g) ] values. Starting with equation 6-2 for MLyn(soln)
= M(H20)63+(aq) and following the same procedure for the gas-phase
M(acac)3 complexes above, an equation relating the difference in
electron attachment energies between M(H20 ) 63+(aq) complexes and M+3(g)
ions is given in eq 6-6.
AGa°[M(H20)63+(aq) ) - ALFSE = AHa°[M+3(g)] + AAHhet,°[M(H20)63+/2+]
” AAHsolv°[M(H2°)63+/2+] " T(ASa°[M(H20 ) 63+(aq)]) 6-6
Values of Dq are available in the literature for M(H20)63+ and M(H20)62+
ions from spectroscopic studies and ALFSE is readily evaluated. In
chapter 5 the relationship between AGa°[MLyn( soln) ] and E° for the
MLyn/(n'15 (soln) redox couple was shown to be -AGa°[MLyn( soln) ] =
F(E°[MLyn/ potential of the standard hydrogen electrode and F is the Faraday

128
constant. Using this relationship, equation 6-6 can be written in terms
of the standard reduction potential of the M(H20)63+/2+ redox couple, eq
6-7.
-FE° - ALFSE = AHa°[M+3(g)] + AAHhet,°[M(H20)63+/2+] - AAHsoly°[M(HgO)63+/2+]
-T(ASa°[M(H20 ) 63+(aq)]) + Eabs°(SHE) 6-7
The terms AAHhet,°[M(H20 ) 63+/2+] - AAHsolv°[M(H20 ) 63+/2+] on the right-hand
side of eq 6-7 correspond to the difference in enthalpy separated by the
two dashed lines drawn through the series of AHhyd°[M+3(g) ] and
AHhyd°[M+2(g) ] values in Figure 6-2, which is a generally smooth trend.
The term ASa0[M(H2O)63+(aq)] contains the intramolecular entropy change
discussed in chapter 4, which is expected to be similar in magnitude to
the values of ASa°[M(acac)3(g)] and therefore small, and the entropy
change resulting from the difference in polarization of the solvent.
The latter contribution is a function of the charge and radius of the
ions involved in the couple and is predicted by the Born equation (eqs
4-13 and 4-14) to vary smoothly. The remaining term is the constant
E°abs(sHE), and therefore all terms except AHa°[M+3(g)] on the right-hand
side of eq 6-7 vary in a smooth periodic manner. The sum of the terms
on the right-hand side of eq 6-7 should therefore reflect the same
periodic trend as AHa°[M+3(g)]. The deviations in the periodic trend
lines between the values of E° for the M(H20 ) 63+^2+ couples and
AHa°[M+3(g)] can therefore be attributed to ALFSE, as was shown above for
the trend in AGa°[M(acac)3(g)] values.
Conclusions
The change in trends in electron attachment energies for complexes
in comparison to the corresponding free ions can be qualitatively
explained through consideration of the effects of ligand field splitting
of the primarily valence d orbitals. In particular the much reduced

129
range of values for AGa° for M = Ti-Co ("2 eV) in comparison to the free
ions ('7 eV) results from preferential stabilization of the reduced
forms of the M(acac)3" complexes for M = Cr, Mn and Co relative to the
M(acac)3. The magnitudes of the AGg° values for the M(hfac)3 complexes
are "50 kcal mol"1 higher than those for the corresponding M(acac)3
complexes and this can be considered a result of a smaller change in
heterolytic bond energy associated with the reduction of the M(hfac)3
complexes.

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BIOGRAPHICAL SKETCH
The author was born in Warrington, Lancashire, England, in
November of 1958. After attending Appleton Grammar School, he left to
work as an analytical chemist at Warrington effluent treatment works for
a period of three years, while attending St. Helens Technical College on
a day release basis. In 1980 he obtained the higher national
certificate in chemistry. Feeling a desire for an academic environment,
the author became a full-time student in 1980 at Preston Polytechnique
Institute, studying for Graduateship of the Royal Society of Chemistry
examinations parts I and II. After gaining a pass at the examinations
in 1982, he returned to work for one year before being accepted into the
graduate chemistry program at Auburn University, Alabama, USA. Aiming
his goals still higher, the author was accepted into the graduate
chemistry program at the University of Florida in 1984.
139

I certify that I have read this study and in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the Doctor of
Philosophy.
David E. Richardson
Associate Professor of Chemistry
I certify that I have read this study and in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the Doctor of
Philosophy.
I certify that I have read this study and in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the Doctor of
Philosophy.
Russell S. Drago
Graduate Research Professor of
Chemistry

I certify that I have read this study and in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the Doctor of
Philosophy.
I certify that I have read this study and in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the Doctor of
Philosophy.
Chemical Engineering
This dissertation was submitted to the Graduate Faculty of the
Department of Chemistry in the College of Liberal Arts and Sciences and
to the Graduate School and was accepted as partial fulfillment of the
requirements for the degree of Doctor of Philosophy.
Dean, Graduate School
August 1990

UNIVERSITY OF FLORIDA
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