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Activation of hydrogen and carbon monoxide by transition metal complexes

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Title:
Activation of hydrogen and carbon monoxide by transition metal complexes
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Miller, James G., 1957-
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English
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viii, 212 leaves : ill. ; 28 cm.

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Subjects / Keywords:
Catalysts ( jstor )
Hydrogen ( jstor )
Imidazoles ( jstor )
Ligands ( jstor )
Phosphines ( jstor )
Rhodium ( jstor )
Silanes ( jstor )
Silica gel ( jstor )
Solvents ( jstor )
Synthesis gas ( jstor )
Carbon monoxide ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Hydrogen ( lcsh )
Transition metal compounds ( lcsh )
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bibliography ( marcgt )
non-fiction ( marcgt )

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Thesis:
Thesis (Ph. D.)--University of Florida, 1985.
Bibliography:
Bibliography: leaves 203-210.
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by James G. Miller.

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Full Text


ACTIVATION OF HYDROGEN AND
BY TRANSITION METAL
CARBON MONOXIDE
COMPLEXES
By
JAMES G. MILLER
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


To my parents, Mary and George Miller, and my wife,
Nan, whose constant support and encouragement made this
work possible.


ACKNOWLEDGEMENTS
I wish to express my deep appreciation to my research
director, Professor Russell S. Drago, for his guidance,
motivation, and understanding during my years at the
University of Illinois and the University of Florida.
A very grateful thank you goes to Professor Glenn C.
Vogel for his encouragement and friendship.
I would like to thank the members of the Drago research
group, both past and present, for their help, discussions
and friendship. Among the group Mike Desmond, Dean Oester,
Pete Doan, Jim Stahlbush and especially Keith Weiss deserve
special thanks. Robert King and Chris Schiriner are
acknowledged for their invaluable assistance with the GC
mass spectrometry and electrochemistry studies,
respectively.
Financial support by the University of Illinois, the
University of Florida and Professor Drago in the form of
teaching and research assistantships is gratefully
acknowledged.
Finally, a very special thanks go to Ginger Solano and
my wife Nan for their patience and help in preparing this
manuscript.
i i i


TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iii
ABSTRACT vi
CHAPTER
I. INTRODUCTION 1
II. ACTIVATION OF MOLECULAR HYDROGEN 4
Introduction 4
Experimental 11
Materials 11
Instrumentation 12
Synthesis 13
Thermodynamic Measurements 14
Hydrogen Gas Flow System 15
Results and Discussion 24
Conclusion 46
III. IMMOBILIZED HOMOGENEOUS CARBON MONOXIDE
REDUCTION CATALYSTS 48
Introduction 48
Experimental 59
Reagents 59
Instrumentation 59
Fixed Bed Flow Reactor 60
Synthesis 63
Results and Discussion 73
Polymer Supported [RuCCO)3I3] and
[HRu3 (C0)lx ]- 73
Synthesis and characterization 73
Catalysis 83
Covalently Supported Ir^CO)]^ 83
Synthesis 83
Infrared characterization 86
Catalysis 94
CH3CI catalyst development 102
IV


Halogen sources 126
GC Mass spectrometry 131
Mechanism 142
Conclusion 146
IV. IMIDAZOLE FUNCTIONALIZED SILICA GEL 149
Introduction 149
Experimental 153
Materials 153
Instrumentation 153
Synthesis 154
Results and Discussion 158
Synthesis Imidazole Support 158
Hydroformylation 167
Conclusion 169
V. SOLUBLE BIMETALLIC COMPLEXES 171
Introduction 171
Experimental 173
Materials 173
Instrumentation 173
Synthesis 177
Results and Discussion 181
Ligand Preparation 181
Metalomers, Synthesis and Characterization 182
Electrochemistry 195
Conclusion 199
VI. SUMMARY AND CONCLUSION 201
REFERENCES 203
BIOGRAPHICAL SKETCH 211
v


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
ACTIVATION OF HYDROGEN AND CARBON MONOXIDE
BY TRANSITION METAL COMPLEXES
By
James G. Miller
December 1985
Chairman: Russell S. Drago
Major Department: Chemistry
Reported here are four studies related to the catalytic
processes involving the activation of carbon monoxide and/or
molecular hydrogen by transition metal complexes. The first
study investigates the process of hydrogen activation by
square-planar rhodium (I) complexes of the formula
(P(p-tolyl)^RhClB where B is P(p-tolyl)^,
tetrahydrothiophene (THTP), pyridine and N-methylimidazole .
Enthalpies were determined for the reaction of the
P(p-tolyl)^ and THTP complexes with H? forming cis
dihydride complexes of the formula (P(p-toly1)^)^RhClBH^.
Attempts to determine enthalpies for the pyridine and
N-methylimidazole complexes were unsuccessful.
The metal-hydrogen dissociation energies determined
from these enthalpies were found to be insensitive to the
ligand variation around the rhodium center.
In the second study, ruthenium and iridium homogeneous
CO reduction catalysts were immobilized on silica gel and
alumina. Ionic attachment of the two ruthenium anions
vi


[Ru(CO).,I,] and [HRu,(CO)^^j to ammonium
iodide functionalized silica gel, as demonstrated by
infrared showed no syngas (CO and H^) conversion up to
175C and 1 atm pressure.
A physical mixture of AlCl^ and Ir^(CO)^
covalently attached to a phosphine silane functionalized
silica gel or alumina was found to selectively produce
CH^Cl from syngas under very mild conditions, 25C, 1
atm pressure. Replacement of AlCl^ as the chloride source
by addition of HCl(g) to the syngas feed enabled production
of CH^Cl with 99% selectively at temperatures up to
100C. The novel chemistry was demonstrated with other
halogen sources: aqueous HC1, Cl^ and HBr (producing
CH,Br). The presence of a Lewis acid and the phosphine
silane linkage appeared to be important for their catalytic
properties.
In the third study a 4(5) substituted imidazole
functionalized silica gel support was synthesized to
heterogenize a homogeneous rhodium imidazole
hydroformylation catalyst. The synthesis utilizes Schiff
base reactions between an aminosilane functionalized silica
gel, histamine and 1,4-dihydroxy-2,5-dibenzaldehyde. The
rhodium metalated support was active for the conversion of
1-hexene but suffered severe metal leaching.
In the fourth study a series of soluble bimetallic
complexes of the formula [M(11)(DIOX)BF^, (M = Cu, Ni,
Zn, Pd; DIOX = bis-4 tert-buty1-2,6-diformy1-pheno1 dioxime)
vii


was synthesized and characterized. These complexes are
formed from analogous insoluble 0-H**0 bridged complexes by
reaction with BF^Et^O. Electrochemical studies were
performed on the Cu(II) BF^ capped complex in acetone and
DMF and illustrated strong metal site interactions.
viii


I. INTRODUCTION
The field of catalysis is one of the most active and
intensely pursued areas of chemistry research. The
overriding goal of this research, driven primarily by
its economic importance, is to develop better and more
efficient catalysts.
Reported here are the results of four studies all
related to catalytic processes (i.e. hydrogenation, carbon
monoxide reduction, hydroformylation) involving the
activation of carbon monoxide and/or molecular hydrogen by
transition metal complexes. These studies focus on two
different aspects of catalysis research: 1) gaining an
understanding of chemical transformations taking place in a
catalytic cycle and 2) developing new and novel transition
metal catalysts. In the first study thermodynamic data
were obtained on the activation of molecular hydrogen by
square-planar rhodium(I) complexes of the formula
[P(p-tolyl) ]2RhClB (B = P(p-tolyl)3, THTP, Py, Helm).
These results provide needed information on the strength of
the metal hydrogen bonds formed upon activation of molecular
hydrogen by a typical hydrogenation catalyst, "Wilkinson's"
catalyst'* and the sensitivity of these bonds to variation
in the ligand environment around the metal center. These
1


2
results also give insight into adverse effects of additives
such a pyridine to the catalytic system.
In the second study immobilized homogeneous transition
metal catalysts were synthesized and tested for their use in
developing selective carbon monoxide reduction catalysts
which operate under mild reaction conditions. A low
pressure and temperature catalytic system was discovered and
described for the conversion of syngas (CO + H^) and HC1
selectively to chloromethane using a bifunctional supported
iridium cluster catalyst. The active catalyst precursor
consists of Ir^(CO)-^ covalently attached to a phosphine
silane functionalized silica gel or alumina and can be
operated in the presence or absence of an MCI-
co-catalyst.
The third study, which relates very closely to the
immobi1ized catalysts used in the previous study, involves
the development of a 4(5) substituted imidazole
functionalized silica gel support. The new support was
designed to heterogenize a reported homogeneous rhodium
imidazole hydroformylation catalyst of the formula
2 3
[Rh( imidazole) ].. The synthesis and characterization
of this new support are reported along with preliminary
tests on the hydroformy1 ation activity of the rhodium metal
loaded support.
The fourth and final study reported deals primarily
with the synthesis and characterization of new soluble
bimetallic macromolecules which might be capable of


3
facilitating bifunctional catalysis similar to that
demonstrated in the second study. These complexes
synthesized are of the formula [M(DI0X)BF^^ (DIOX =
bis-4-tert-butyl-2,6-dif orinyl-phenol dioxirne and M = Cu Ni ,
Zn, Pd) and contain two metal centers in close proximity
allowing metal site interactions.


II. ACTIVATION OF MOLECULAR HYDROGEN
Introduction
Activation of molecular hydrogen by metals is an
important fundamental process with relevance to many
catalytic systems (i.e. hydrogenation of olefins,4
hydroformylation,^ and reduction of carbon monoxide by
H^) and to storage of by dissolution in metals.
In order to develop better and more efficient
catalysts, it is important to determine what metal hydrogen
bond dissociation energies are needed to affect desired
chemical transformations. For example, a transition metal
hydride complex will not be a good hydrogenation catalyst if
its M-H bond strengths are so large that it is unable to
easily transfer hydrogens to an olefin.
To date, very little thermodynamic data have been
reported in the literature regarding metal hydrogen bond
dissociation energies and their dependence on various
ligands in the metal coordination sphere. The reaction of a
series of square planar rhodium (I) complexes of the formula
[P(p-tolyl)3]2RhClB (B=P(p-tolyl)3, THTP, Py, Melm)
with molecular hydrogen forming six coordinate rhodium
(III) dihydride complexes (Equation 1) provided an excellent
opportunity for this type of study.
4


5
[P(p-tolyl)3 ]2RhClB + H2< [ P ( p toly 1), ] 2 RhCl B (H, ) (1)
The complex [P(p-tolyl)3]2RhClB, (where B=P(p-toly1)^)
often termed "Wilkinson's catalyst," has been extensively
studied since it was first reported to be a good
hydrogenation catalyst by Wilkinson et al.1 in 1966. To
this date, a number of studies and mechanistic schemes have
8 i 2
been published. The most recent was proposed by
13 14
Halpern et al. and is shown Figure 2-1 where
L = P(p-tolyl) 3 or PCC^H^)^, S = solvent, and C = Cn
represents some non-sterically hindered unconjugated olefin.
In concentrations of up to 0.1M excess phosphine the
predominant catalytic pathway is not through direct
hydrogenation of RhClL^ I but through a dissociative
pathway where RhClL^ dissociates a phosphine generating
the unsaturated three coordinate species RhClL^ II. This
was found to activate H2 1 04 times faster than RhClL^
generating another coordinately unsaturated complex
RhClL3(H)2 III which then reacts with an olefin giving
the six coordinate complex IV. Stepwise hydrogen transfer
to the olefin produces the alkane product and also
regenerates the three coordinate complex II. The catalytic
cycle then continues along the pathway contained in the
dotted circle.
A number of studies have been published attempting to
correlate changes in the ligand environment around the


Figure 2-1. Mechanistic scheme proposed for the
hydrogenation olefins by "Wilkinson1
Catalyst."


7
L L
X ^
Rh
C,^
I
S
-L
\ /
-cc-
/
H
H
l v
Rh
Cl^ I
:c=c:
H
L S
Rh
Cl^
I
c=c.
s
L V H
^ 1 ^
Rh
Cl^ ^ L
S
nr


8
rhodium center to catalytic activity. Most of these studies
involved changing all three phosphines with other phosphines
and other 2 electron donating bases. When a series
of para-substituted aryl phosphines were used, it was found
that catalytic activity increased as the electron donating
ability of the phosphine increased. This could be due to
the more electron donating phosphines making the rhodium
more basic improving its ability to activate H-, (as well
as to back bond into olefins).
When alkyl phosphines were used, which are even more
electron donating than aryl phosphines, catalytic activity
was diminished. These results can be interpreted in a
number of ways. First, the alkyl phosphines could be making
the rhodium center so basic that the rhodium hydride and
rhodium olefin complex are becoming too stable. Second,
steric factors may also be playing an important role. The
less bulky more electron donating phosphines may be binding
too tightly to the rhodium center preventing the necessary
phosphine dissociation steps that provide important
coordinative unsaturation. When the bulky aryl phosphines
19
were used, crowding around the metal center may be
increasing the tendency for ligand dissociation.
Further studies have used N, S, As and Sb
donors^^^^^ around the rhodium center. Also, it was
reported1 that large excesses of pyridine, acetonitrile
and various sulfur donors added to solutions of
RhCl ( P ( C^H;- ) j j greatly reduce catalytic activity.


9
Due to the complexities of a catalytic system it is
difficult to predict exactly what reactions are being
affected by variations imposed on the system unless each
catalytic reaction step can be studied separately. This
study will hopefully give some insight into one segment of
the catalytic reaction, that is the effects of ligand
variation on the activation of molecular hydrogen by rhodium
complexes with structures similar to Wilkinson's.
A convenient and fairly simple method for making
derivatives with one ligand around the rhodium center of
Wilkinson's catalyst being varied was found making use of
the dimer bridge cleavage reaction shown in Equation 2.
2 2 2 3
Calorimetric studies on this
P Cl P B
\ \ \ /
Rh Rh + 2B < 2 Rh (2 )
/ \ / \ / \
P Cl P P Cl
(P = P(p-tolyl)3)
and two other chloro bridged dimer systems [RhCl(CO)2^^
2 5
and [RhCl(COD)^have previously been reported by
the Drago research group.
The bridge cleavage reaction of the phosphine dimer
([RhC1(P(p-toly1),)^]2) was found to occur with nitrogen,
phosphorus and sulfur donors. Attempts using oxygen donors
were unsuccessful. By way of and ^P NMR the
geometric structure of all the monomeric base adducts formed
were found to be the same; that is the base occupied a


10
position cis to the chlorine, as shown in Equation 2. Heats
obtained for the bridge cleavage reaction were incorporated
into the E, C and W correlation (Equation 3) and E^
and parameters were generated for the three coordinate
acid (P(p-tolyl)j)2RhCl.
- AH = EaEb + CA CB + W (3)
The monomeric base adducts generated in solution were
also shown to react with molecular hydrogen at ambient
temperature and pressure (Equation 1). The six coordinate
rhodium (III) dihydride complexes formed (shown below) were
found to have the same geometric structure, again using ^H
and NMR. The two inequivalent hydrides end up cis to
H
Cl
x x.
H
each other and the two equivalent phosphines occupy trans
pos itions.
This study deals specifically with the thermodynamic
aspects of the activation of molecular hydrogen by
Wilkinson's catalyst and its derivatives. Determination of


11
theAH for Equation 1 will provide us with a better
understanding of the influence of donor strength on the
activation of molecular hydrogen and on the average Rh-H
bond strength.
In addition, the resulting thermodynamic data could
possibly be entered into the E, C and W correlation and E^
and parameters could be determined for the five
coordinate acid "(P(p-tolyl)^2RhCl(H)2." By comparing
these E and C parameters to the E and C parameters of the
three coordinate acid "(P(p-tolyl)^RhCl," the effect of
oxidative addition of H? on the acidity of the rhodium
center could be quantitatively determined.
Experimental
Materials
Toluene was dried and degassed by first refluxing over
CaH^ for 24 hours, collected by distillation under
and then subjected to freeze pump thawing (a minimum of 5
cycles using a mercury diffusion pump). It was then stored
in an inert atmosphere box until needed. Rhodium
trichloride 3H20 was purchased and used without further
purification.
All bases used in this study were purchased and
purified by the following methods. Tri-p-tolylphosphine was
recrystallized in hot absolute ethanol followed by drying


12
under vacuum. Pyridine (Py) was stored over KOH pellets
overnight, then distilled from BaO under (middle
fraction taken, boiling range 112.0 112.5C).
Tetrahydrothiophene (THTP) was fractionally distilled over
CaH^ at atmospheric pressure. N-methylimidazole was
fractionally distilled over CaH^ at 10 mmHg pressure and
the middle fraction taken. Dimethylthioformamide was dried
over 4A molecular sieves. All liquid bases were degassed by
freeze pump thawing.
Ethylene, hydrogen and nitrogen gases used were
obtained from Linde (Union Carbide); the hydrogen and
nitrogen were of ultra-high purity ( 2 ppm 0^, 3 ppm
moisture).
High capacity oxygen traps were purchased from L.C.
Company, Inc. These were designed to remove 0 to below
0.1 ppm with a gas flow of less than 3 liters per minute.
The traps contain a Mo based indicator which is blue-green
when activated and grey when spent. The traps were
periodically regenerated by placing them in a Lindberg
(model 123-8) tube furnace at 375C while passing Hgas
through them at a rate of 30 cc/min for 20 minutes.
Instrumentation
All air sensitive manipulations were performed in a
Vacuum Atmosphere Co. model HE-43-2 inert atmosphere box,
in specially designed Schlenck-ware glassware. Elemental


13
analysis was performed by the Microanalytical Laboratory,
University of Illinois, Urbana, Illinois.
Electronic absorption spectra were taken on a Cary
14-RI spectrometer equipped with a Varian constant
temperature chamber in the sample compartment. The chamber
was coupled to a Braun Thermoboy circulating temperature
bath which will maintain a constant temperature to
_+0.2C. For temperatures below room temperature a cold
slush bath was added to the circulating system. The bath
consisted of 1/4" x 10' copper tubing coil suspended in a
dewar containing any number of solvent/CO^ or solvent/N^
2 7
slushes depending on the temperature desired. Methanol
was used as the circulating liquid at low temperatures to
prevent freezing and the sample compartment was continuously
purged with to prevent moisture from condensing on the
sample cell.
Synthesis
Di-cL-chlorotetrakis(ethylene)dirhodium(I),
[Rh(C)^C1 ] 7, was prepared according to a method
2 8
reported by Cramer. A solution of 0.6 g (2.28 mmoles)
RhCl^* 3H20 dissolved in 1 ml of H^O and 7.0 ml
methanol was added to a 125 ml Parr pressure bottle
containing a magnetic stir bar. The mixture was then purged
5 times with ethylene and finally pressurized to 20 psi.
After 15 hours of stirring the solution had changed color
and an orange-yellow precipitate had formed. The solid was


14
filtered and washed with anhydrous methanol in a filled
glove bag and dried for 2 hours over P2O,-. (Caution,
vacuum drying will result in the loss of ethylene from the
complex.) The complex can be stored indefinitely under
at 0C.
Di-a-chlorotetrakis(tri-p-tolylphosphine)dirhodium(I),
[Rh(P(p-tolyl)^)^C1]2 was prepared by combined methods
8 1
reported by Tolman et al. and Wilkinson et al. In an
inert atmosphere box 0.266 g [ Rh( C2H4 ) ?C1 ]-, 0.85g of
freshly recrystallized P(p-tolyl)^ and 17 ml toluene were
placed in a 50 ml round bottom flask equipped with a Vigreux
column. The resulting solution was refluxed with stirring
for 5 hours. While still warm, 35 ml of hexanes were added
and the solution was allowed to cool. The orange
precipitate that formed was filtered, washed with hexanes
and dried for 12 hours under vacuum. This complex is found
to decompose slowly with time and can be purified by
repeated recrystallization in toluene followed by addition
of hexanes. Analysis: C, 67.6; H, 5.7; Cl, 5.0.
Theoretical: C, 67.5; H, 5.7; Cl, 4.8.
Thermodynamic Measurements
Spectrophotometric titration was used to determine the
equilibrium constant of the following reaction:
(P(p-tolyl)3)2RhClB + H2 ~~ ( P ( p-t oly 1 )3 ) 2 RhCl B (H )2 (4)


15
Due to extreme 0? sensitivity of the above reaction a
special hydrogen gas flow system was used to vary the
hydrogen partial pressure. A series of preset H-,/N^ gas
mixtures were bubbled through a 0.1 cm UV-vis cell
containing a toluene solution of (P(p-toly1)^^RhClB.
Absorbance changes of the hydrogenated complex in the
visible range (350-650nm) were recorded after equilibrium
was reached with each hydrogen partial pressure.
Equilibrium constants were determined with the
2 9
Gasuptake program developed by Beugelsdijk in which the
best K-'*' and (Eo-E) were simultaneously determined. By
use of the best fit (Eo-E) calculated for each temperature
equilibrium constants were generated for each absorbance
change. These K's were then used in a van't Hoff analysis
to determine AH. In determination of 90% confidence
intervals for AH, a degree of freedom was subtracted for
each temperature used to account for holding the best fit
(Eo-E) constant.
Hydrogen Gas Flow System
A specially designed gas flow system was assembled as
shown in Figure 2-2. Hydrogen and nitrogen gas was first
passed through L.C. Company 0^ traps removing 0^ up to
0.1 ppm. The gases then enter a Matheson (Model 7352)
rotometer fitted with no. 610 tubes where the gases are
accurately mixed to the desired N?/H, ratios. The
no. 610 tubes are the most sensitive flow meters available


Figure 2-2. Gas flow system.


ja 7-ii
Brass Valves


18
from Matheson and are essential for accurate determination
of N^/H^ ratios.
The mixed gas leaving the rotometer enters a brass
manifold made up of Swaglok hardware including five gas
valves. From here the gas is directed to a specially
designed bubbler containing a toluene solution of the
rhodium chloride dimer. The bubbler saturates the gas with
toluene so that when it is bubbled through the toluene
solution in the UV-vis cell, there is no appreciable
evaporation. The function of the oxygen sensitive rhodium
chloride dimer in the bubbler was to act as a final 07
trap.
The gas now saturated with toluene was bubbled through
the bottom of a highly modified 0.1 cm pathlength barrel
UV-vis cell (Figures 2-3, 2-4) situated in the thermostated
source compartment of a Cary 14 spectrophotometer. The
special cell contained a toluene solution of the solution
generated monomeric rhodium base adduct. Gas exiting the
cell was bubbled through a mineral oil bubbler which
maintained a constant internal pressure in the system. A
mercury monometer present in the system was used to
determine the internal pressure.
Solutions of the various monomeric base adducts were
generated by adding enough of each base to a rhodium dimer
solution to cause greater than 95% cleavage of the dimer.
The amount of each base added was based on equilibrium
30 2 3
constants reported by Farris and Hoselton for the


Figure 2-3. UV-cell.
A. lmm pathlength barrel cell
B. #7 O-ring joint
C. Teflon needle valves


20
Side
Fron t


Figure 2-4. UV-vis cell holder.
A. Thermostated cell holder
B. UV-vis cell
C. Aluminum cell holder
D. Rubber liner


22


23
bridge cleavage reaction. The general operating procedure
of the hydrogen gas flow system is described below in an
example experiment (refer to Figure 2-2).
The UV-vis cell and the toluene bubbler were removed
from the flow system and placed in an inert atmosphere box.
The cell was filled with a toluene stock solution that was
2.02 x 10"^M in [Rh(P(p-tolyl)^Cl]2 and 8.111 x 10 2M
in P(p-tolyl)j. The toluene bubbler was loaded with
toluene that contained a spatula or two of
[Rh(P(p-tolyl)?C1]^. The teflon valves were closed
on both the cell and the bubbler. The cell and bubbler were
then removed from the inert atmosphere box and placed back
into the flow system.
Having all the valves closed except for valves #3, 6
and 9, the system was evacuated by opening valve #10 which
was connected to a vacuum pump. After closing valve #10,
the system was then purged with by opening valve #8.
The evacuation-purge cycle was repeated a minimum of five
times. Following the final purge with valves #8 and
#6 were closed and valves #4, 5 and 11 were opened.
Valve #8 is opened fully and the rate of N2 bubbling
was now controlled by the rotometer valve. Valve #9, which
is the major bypass valve, is slowly closed until a
satisfactory bubble rate is achieved in the toluene
bubbler. Too high a rate may cause toluene to foam over
into the built in trap.


24
Valves on the cell, #1 and #2, were then opened fully.
Valve #3, a minor bypass valve, was slowly closed until the
desired cell bubble rate was achieved, about 1 bubble per
second. Too rapid a bubble rate may cause evaporation.
After the rhodium monomer solution had come to equilibrium
with the N? in the system, the valves on the cell were
closed and the visible spectrum was recorded.
Valve #3 was opened fully and the rotometer valves were
adjusted to give the first desired hydrogen partial
pressure. The bubbling through the toluene bubbler was
adjusted again by valve #9 and the system was allowed to
purge for 30 minutes. Following purging, the cell valves
were opened and bubbling through the cell solution was
adjusted using valve #3. Once the cell solution had come to
equilibrium, indicated by no further change in the
absorbance spectrum, the cell valves were closed and the
visible spectrum was recorded. This same procedure was
followed for each additional hydrogen-nitrogen gas mixture.
The rotometer was calibrated prior to the experiment
using a soap bubble flow meter connected to valve H7.
Results and Discussions
Fairly extensive thermodynamic and structural studies
have previously been done by Farris'^ and Hoselton25 on
the bridge cleavage reaction (Equation 2) of the chloro


25
bridged dimer [RhCl(P(p-toly1)2 with various
sulfur, nitrogen and phosphorous donor bases. Equilibrium
constants and heats of reaction obtained for the reaction
are shown in Table 2-1.
Based on these results monomer solutions used for the
reaction with hydrogen (Equation 1) were made by adding a
sufficient quantity of base to a rhodium dimer solution to
cleave the dimer by greater than 95%. The ratios of base to
dimer concentration suggested by Farris were as follows:
P(p-tolyl)^, 40:1; THTP, 60:1; pyridine, 40:1. The
resulting monomer solutions were then loaded into the cell
of the specially designed flow system.
Great care was taken to exclude 0^ while preparing
the monomer solutions because of their extreme oxygen
sensitivity. Fresh monomer solutions were made before each
experiment in an inert atmosphere box. The rhodium dimer
which was also oxygen sensitive had to be recrystallized
periodically to maintain its purity.
Previously, Farris50 had attempted to determine heats
for the reaction of the various base monomers with molecular
hydrogen using a variable temperature spectrophotometric
titration method utilizing a static gas system. This proved
unsuccessful mainly due to problems with oxygen
contamination.
An alternative to a static type system is a gas flow
type system which was developed for this study (Figure 2-2)
and described in detail in the experimental section. The


26
Table 2-1. Thermodynamic Results for the Interaction of
[RhCl(P(p-tolyl33)2with Various Bases at
24 + 2C .
Base
a
ah
a
K
b
K (spec )
P(p-tolyl)3
c d
-4.7 + 0.3
e
Large
-
Pyridine
- 4.9 + 0.2
Large
1 8 3 j+ 2 2
THTP
-1.9+0.2
(1.0+0.4)xl02
-
N-methylimidazole
-6.6+0.2
(2.4+2.0)xl04
-
a Determined by Calorimetry.23 b Determined
spectrophotometrica1ly.^0 c Units of Kcal/mole of monomer
formed, d Reported errors are standard deviations.
e Keq. is unknown but assumed to be very large for purpose
of calculating AHav.


27
main advantage of this system is that a positive pressure of
and is maintained throughout an experiment which
reduces the chance of 0^ leaking into the system from the
outside atmosphere. One disadvantage of a flow system is
that care must be taken to prevent solvent evaporation due
to continuously bubbling the various gas mixtures
through the cell solution. This potential problem was
solved first by maintaining a slow continuous bubble rate
through the cell solution and second, by placing a toluene
bubbler in the gas line before the cell. This aided by
prior saturation of the gas with toluene
minimizing any solvent evaporation due to bubbling gas
through the cell.
In order to test the flow system a toluene solution of
air stable tetraphenylporphyrin solution was placed in the
cell of the flow system. After 2 hours of continuously
bubbling N2 through the solution, there was no significant
change in its UV-visible spectrum indicating that the
toluene bubbler was effectively preventing solvent
evaporation.
The changes that occurred in the electronic spectra
upon bubbling various partial pressures of hydrogen through
solutions of (P(p-toly1)^)2RhClB are illustrated in
Figures 2-5 and 2-6 for the bases P(p-tolyl)^ and THTP
respectively. In both cases the shoulder (centered at
430nm for P(p-tolyl)^ and 420nm for THTP) on the side of


Figure 2-5. UV spectrum of a toluene solution of 1.86x10'%
[RhCl(P(p-tolyl)3)2]2 > and 7.47x10'%
P(p-tolyl)3 at 35.0C in equilibrium with
various pressures of H2. (1: Ph2 = 0-00 atm,
2: Pjq2 = 02 3 atm, 3: P^2 = *045 atm,
4; Ph2 = .075 atm, 5: P^2 = -145 atm,


2^
\ O
o


Figure 2-6. UV spectrum of a toluene solution of 2.98xlO^M
[RhCl(P(p-tolyl)3]2 > and S.79xlO"2M THTP at
10.0C in equilibrium with various pressures
of H2- (1: Ph2 = 0.00 atm, 2: P^2 = .015 atm
3: PH2 = *102 atm, 4: Pjq2 = .217 atm
5: P^2 = .965 atm.)


Absorbance
31
Wavelength, nm


32
a large charge transfer peak decreased in intensity as the
concentration of increased.
An isobestic point was observed in the P(p-tolyl)^
system at about 350nm probably indicating that only two
chromophors were present in solution and that the rhodium
monomer was being cleanly converted into the six coordinate
cis-rhodium dihydride complex. This provided further
evidence supporting what had previously been shown by NMR
studies of the reaction. (Caution must be taken not to rely
solely on the appearance of an isobestic point. An
additional experimental method should be used to determine
the actual reaction taking place.)
The spectral data obtained were analyzed using the
Rose-Drago^1 equation (Equation 5)
3 2
which was modified for the hydrogen uptake experiment.
In this equation is the hydrogen partial pressure
bubbled through the solution, b is the pathlength of the
cell, A is the initial concentration of the acid (Rh
o
monomer), A is the absorbance of the cis dihydride complex,
A is the absorbance of the acid solution (with no H7
present), (Eo-E) is the difference in the molar absorptivity
between the hydrogenated and monohydrogenated complex and
K 1 is the inverse of the equilibrium constant for the
reaction.


33
The spectral data and the best determined K and (Eo-E)
values at various temperatures are listed in Table 2-2 for
the bases P(p-tolyl)j and THTP. An equilibrium constant
8 -1
previously reported by Tolman et al. of 40 +_ 3 atm at
25C corresponds well with the results of this study where
at 30.1C a value of 29.9 _+ .26 atm ^ was obtained.
Attempts to study the pyridine adduct produced
inconsistent results. This system, unlike the previously
described base adduct systems, was not as well behaved and
presented a number of complications. The first complication
encountered was the extreme 0^ sensitivity of the pyridine
system. Additional precautions to exclude 0^ had to be
taken during the generation of the monomer solutions and
when flushing the flow system.
Initial spectral results established that the
equilibrium constant for the pyridine system was at least an
order of magnitude greater than was observed for the
P(p-tolyl)^ and THTP adducts. This was a problem because
the lowest possible partial pressure that could be
accurately delivered by the rotometer was converting most of
the pyridine monomer into the hydrogenated form.
To overcome this problem, another Matheson rotometer
was added to the flow system. The rotometers were connected
in series as illustrated in Figure 2-2. Rotometer 1 diluted
the with N^. The mixture then entered the second
rotometer reducing the H- concentration with once
again. The double dilution feature of the system allowed


34
Table 2-2. Thermodynamic Data for the Reaction of
RhClB(P(p-tolyl)3)2 + H2RhClB(P(p-tolyl) 3) 2H2 .
B
Temp (C)
a
K
P(p-tolyl)3
9.0
113.7
30.1
29.9
35.0
24.4
44.0
12.2
53.8
7.27
b
c
AH = 11.0 +
. 5 Kcal/mole
THTP
10.0
77.4
15.0
47.6
20.6
33.9
30.0
21 5
40.0
13. 2
50.0
5.91
b
c
AH = 11.6 + 1
.0 Kcal/mole
a Best fit K. b Determined by van't Hoff analysis,
based on generating an equilibrium constant for each
absorbance change after the best Eo-Ewas determined and
held constant. c 90% confidence interval.


35
for the accurate delivery of the very low H^N., ratio
gas needed.
A problem encountered which was mainly responsible for
the inconsistent results obtained was the observation of a
slow secondary reaction occurring during the course of the
hydrogen uptake experiment. As seen in the other base
systems, reduction in the shoulder absorbance was observed
on exposing the pyridine monomer solution to various H?
partial pressures. Once the solution had come to
equilibrium with a hydrogen partial pressure, the shoulder
absorbance increased slowly with time instead of remaining
constant. This phenomenon is attributed to a slow secondary
reaction taking place, possibly due to the presence of a
large excess of pyridine in solution with the newly formed
rhodium dihydride complex. (As in the pyridine
experiments, similar problems were encountered with the
1-methy1imidazole adduct experiments.)
The two systems that could be investigated
(P(p-tolyl)^ and THTP) fortunately provided a substantial
variation in the strength of binding to the Rh(I) center.
Enthalpies of hydrogen binding were determined by use of the
van't Hoff equation where a plot of -RlnK vs. 1/T yields a
straight line with a slope of AH and an intercept of AS.
-R Ln K = AH AS
T
(6)


36
Due to the large error limits involved with
calculating AH from a plot of only five or six points
corresponding to K at each temperature, a method suggested
by Breese^ was employed to utilize all of the data
obtained in the equilibrium constant experiments. His
method involves calculating the best K and (E -E) at each
temperature. The best (E -E) at a specific temperature is
then substituted into the Rose-Drago equation and an
equilibrium constant is calculated for each absorbance
change. Thus a number of equilibrium constants were
determined at each temperature (Table 2-3) instead of only
one. The end result was a AH with a much smaller error
limit. Care must be taken in determining standard
deviations to reduce the degrees of freedom by one for every
temperature to account for fixing the value of (Eq-E).
The van't Hoff plots obtained are shown in Figures 2-7 and
2-8 respectively for the P(p-tolyl)^ and THTP systems.
The enthalpies obtained are shown in Table 2-2. These
enthalpies can be combined with the heat of dissociation of
H^ to produce the average metal-hydrogen bond dissociation
energies (Table 2-4).
RhClB(P(p-tolyl)3)2(H)2 > RhClB(P(p-toly1)3)2 + H2 (7)
H2 >2H- (104.2 kca1 mole-1) (8)
RhClB(P(p-tolyl)3)2(H)2 >RhClB(P(p-toly1)3)2 + 2H (9)


37
Table 2-3. Thermodynamic Data on
RhCl(P(p-tolyl )3)2 B + H2 <>RhCl(P(p-tolyl)3)2BH2.
B
(Rh)(M) Pu (atm) Abs K
2
P(p-tolyl)3
Temp.
Temp.
Temp.
Temp.
Temp.
9.0C
4.05
X
10 "3
. 0246
.356
108.5
(Eo-E)a = 1209
4.05
X
10"3
. 0490
.421
125.0
Ka = 113.7
4.05
X
10"3
.0813
.444
119.7
CSD =3.8
4.05
X
103
.156
.465
120.6
MSD/CSDb =1.4
4.05
X
103
.392
.477
96. 2
4.05
X
103
. 981
.483
74. 1
30.1C
4.05
X
10 3
.0237
.158
29.3
(Eo-E) = 951.3
4.05
X
10-3
.0474
.227
30. 2
K = 29.9
4.05
X
10'3
. 0786
.270
29.8
CSD = .26
4.05
X
103
.151
.317
30. 7
MSD/CSD =1.5
4.05
X
10"3
.379
.354
29.9
4.05
X
10'3
.948
.371
27.4
35.0C
3.72
X
10 "3
. 0227
.135
21 8
(Eo-E) = 1095
3.72
X
10"3
.0454
.221
26.1
K = 24.4
3.72
X
103
. 0752
.267
25.3
CSD = .85
3.72
X
10 "3
.145
.318
24. 6
MSD/CSD =1.5
3.72
X
10"3
.363
.364
23.1
44.0C
4.05
X
10'3
. 0224
.087
12.1
(Eo-E) = 1007
4.05
X
10'3
.0449
.141
11 8
K = 12.2
4.05
X
10"3
.0741
.194
12.2
CSD = .19
4.05
X
103
.143
.263
12. 7
MSD/CSD =1.7
4.05
X
103
.359
.334
12.6
4.05
X
103
.898
.371
11.2
53.8C
4.05
X
10 "3
. 0423
.090
6.3 7
(Eo-E) = 1047
4.05
X
10'3
.0701
.139
6.96
K = 7.27
4.05
X
10 ~3
.135
.217
7.78
CSD = 3.7
4.05
X
10'3
.338
.310
8.04
MSD/CSD =1.9
4.05
X
10'3
.844
.358
6.4 1


38
Table 2-3. Continued
B
(Rh)(M)
(atm )
Abs
c
K
THTP
Temp. = 10.0C
5.66
X
10 3
.0147
.256
78.0
(Eo-E ) = 847
5.66
X
10
.102
.423
73.6
K = 77.4
5 66
X
10 "3
.217
.453
79.0
CSD = .99
5.66
X
103
.371
.464
81 2
MSD/CSD =1.2
5.66
X
10"3
.966
.474
90. 9
Temp.
= 15.0C
6 54
X
10"3
.0147
.178
47. 1
(Eo-E) = 66 7
6.54
X
10 "3
.102
.365
50.0
K = 47.6
6.54
X
10 "3
.217
.397
46.2
CSD = .94
MSD/CSD = 1.4
6 54
X
10"3
.371
.412
45.3
Temp.
= 20.6C
4 75
X
10 _3
.0144
.078
33. 6
(Eo-E) = 505
4.75
X
10'3
. 0456
.144
33.0
K = 33.9
4.75
X
10"3
.0993
.188
36. 4
CSD = .68
4.75
X
10"3
.212
.211
34. 4
MSD/CSD =1.5
4.75
X
10 3
.363
.222
34 3
4.75
X
103
.946
.231
27 6
Temp.
= 30.0C
5 14
X
10'3
.0142
.058
18.5
(Eo-E) = 541
5.14
X
10'3
.0986
.195
23.8
K = 21.5
5.14
X
103
.210
.229
22.2
CSD =1.1
5.14
X
10-3
.359
.245
20.6
MSD/CSD =1.8
5.14
X
103
.932
.262
17.5
Temp = 40.0C
5.04
X
lO3
.0136
.030
12.1
(Eo-E) = 4 4 2
5.04
X
10"3
.0946
.113
12.1
K = 13.2
5.04
X
103
.202
.159
15.0
CSD = .31
5.04
X
103
.344
.180
16.53
MSD/CSD = 2.2
5.04
X
10'3
. 898
.189
9. 3
Temp .
= 50.0C
5.98
X
10 3
.0131
.018
2.69
(Eo-E) = 883
5.98
X
10 3
.0912
.190
6. 1 8
K = 5.91
5.98
X
10"3
.194
.283
5.95
CSD = .31
5.98
X
10'3
.331
.350
5.93
MSD/CSD =2.2
5.98
X
103
.864
.440
5.80
Best
fit K and (Eo-E).
b CSD
i s
conditiona1
s tandard
deviation and MSD is marginal standard deviation for best
fit K. c Equilibrium constant for each absorbance change
after best fit (Eo-E) was determined and held constant.


Figure 2-7. Van't Hoff plot for the P(p-tolyl)3 system.


40
o


Figure 2-8 .
Van't Hoff plot for the THTP system.


Ln K
42
o


43
Table 2-4. Average M-H Bond Energies.
Compound AH (av.M-H) Kcal/mole
Rh(P(p-tolyl)3)3Cl(H)2
57.6 + .3
Rh(P(p-tolyl)3)2(THTP)Cl(H)2
57.9+ .5
Ir(CO)XL2H2 3
57-61
b
Co-H
39 + 6
a L. Vaska and Werneke.-^ b j. Beauchamp and
Armentrout ^5


44
Comparing the values obtained for the two base
systems, it is immediately apparent that within
experimental error the average metal-hydrogen dissociation
energies are identical. Thus the rhodium-hydrogen bond
strength was found to be insensitive to varying one ligand
around the rhodium center.
Based on the observation that two vastly different
bases (P(p-tolyl)^ and THTP) had little or no effect on
the Rh-H bond strength, it is probably safe to assume that
other donor bases, such as pyridine, would also have little
effect on the Rh-H bond dissociation energy. Thus the
adverse effects the addition of pyridine (mentioned in the
introduction) has on hydrogenation by Wilkinson's catalyst
is probably due to factors other than those affecting the
catalyst's metal hydrogen bond strength.
A variable temperature ^HNMR study reported by
2 2
Hoselton et al. showed that that following kinetic
process was taking place in the presence of excess pyridine
H
K
H
(10)
B
Cl
B = Py
The pyridine which is trans to a hydride was shown to
exchange with free pyridine in solution. A proposed
intermediate in the reaction was a trigonal bipyramid


45
"Rh(P(p-tolyl),)7C1(H)species. The incoming
pyridine could attack a position trans to either hydride
which would account for the observed averaging of the two
inequivalent hydride resonances with increasing temperature.
A similar kinetic process was reported for an analogous
Wilkinson's catalyst system, Rh( P ( C^Hj-) ^ )jCl (H) 2 > by
O
Tolman et al. The first order rate constants observed for
exchange of pyridine and P(C^H^)^ for the similar
intermediate were 50 sec ^ and 1000 sec ^ respectively at
25C. This ligand exchange process serves a very
important role in the proposed mechanism of Wilkinson's
catalyst in that it provides an important open coordination
site for the binding of an olefin. The fact that the rate
of ligand exchange involving pyridine is an order of
magnitude smaller than that observed for PtC^Hj.), may
account for added pyridine having adverse effects on
catalytic activity due to efficient competition for the
olefin binding site by pyridine.
The metal hydrogen bond energies determined can be
compared to others reported in the literature (Table 2-4).
In a study"^^ 0f the influence of ligand variation in
the system IrCCCOXL^ (where L is a series of phosphines
and X is Cl Br and I ), enthalpies of
hydrogenation of 2.7 to 18.1 kcal mole ^ were measured
corresponding to average metal hydrogen bond energy
variations of 55 to 61 kcal mole ^. The gas phase neutral


46
Co-H bond dissociation energy, determined by ion beam
techniques,^ was reported as 39+_6 kcal mole ^.
Conclusion
The main purpose of this study was to investigate the
process of hydrogen activation by transition metals and to
understand what effect ligand environment has on the metal
hydrogen bond dissociation energy.
The enthalpy of hydrogen activation by
Rh(P(p-tolyl)2C1B was obtained for B = P(p-tolyl)^
and THTP. Attempts to determine enthalpies for pyridine and
N-methylimidazole systems were unsuccessful. The enthalpies
that were obtained were used to determine average metal
hydrogen bond dissociation energies. This provided a good
estimate of the hydrogen bond energies associated with a
good hydrogenation catalyst (Wilkinson's catalyst) and with
one of its derivatives. It also greatly increased the
amount of available data presently in the literature.
The two bases THTP and P(p-tolyl)^ fortunately were
substantially different so that the effect of ligand
variation could be observed. The equilibrium constants
obtained for Equation 1 parallel the basicities of the two
bases toward the rhodium (I) center. However, the
enthalpies obtained for the two systems were remarkably
3 7
independent of the donor strength. Thus the average


47
meta1-hydrogen bond energy was found to be insensitive to
differences in the two ligands. Assuming this result could
be extended to the pyridine system, the adverse effects of
adding pyridine to the catalytic system are probably not due
to pyridine's effect on the catalyst's metal hydrogen bond
strength but more likely due to pyridine blocking important
coordination sites on the catalyst.
A final outcome of this study was that a convenient
method was developed for the determination of enthalpies of
hydrogen activation.


III. IMMOBILIZED HOMOGENEOUS CARBON MONOXIDE
REDUCTION CATALYSTS
Int roduc tion
Immobilization of homogeneous transition metal
catalysts on various organic or inorganic supports, often
termed "hybrid"^ or "HETMETCO"^ (heterogenized
transition metal complex) catalysts, is presently a very
exciting and active field of catalysis research. The over
riding goal in this area of research is to combine the
advantages of heterogeneous and homogeneous catalysts, while
minimizing their inherent deficiencies. A fair number of
articles have been published reviewing the growing volume of
reported studies involving synthesis, characterization and
catalytic properties of supported homogeneous catalysts'^ ^
A list showing the major advantages of heterogeneous
vs. homogeneous catalysts is given in Table 3-1.
Heterogeneous catalysts, viewed by many as being first
generation catalysts, have been widely used in industry for
many years. One of the major advantages of these catalysts
is their ease of separation from reaction products. Other
advantages are that heterogeneous systems are generally more
thermally stable and less corrosive than homogeneous
systems. A major drawback that has hindered the development
of heterogeneous catalysts has been the limited number of
48


49
physical techniques available to characterize these
systems. Although numerous studies over the years have
revealed, little information about the actual active
catalyst species, recent advancements in surface techniques
such as SEM, ESCA, XPS, Auger etc. have provided a better
understanding of the nature of these catalysts.
Table 3-1. Advantages of a Homogeneous Versus Heterogeneous
Catalysts.
Homogeneous
vs.
Heterogeneous
1.
more active
1.
separation of catalyst
from product
2.
reproducible
2.
minimizes reactor
corrosion
3.
milder operating
conditions
3.
more thermally stable
4.
characterization
5.
more selective
Homogeneous catalysts, termed second generation
catalysts, are in many ways superior to heterogeneous
systems. These catalysts are generally more active, more
selective, and because these catalysts are derived from
discrete soluble transition metal complexes they lend
themselves to study by a large number of physical methods.
They have the advantage that their properties can be widely
varied by changing the ligand environment around the metal


50
center and because the composition of the catalyst or
catalyst precursor is known these systems are very
reproducible.
Industrially, homogeneous catalyst systems are much
harder to handle then heterogeneous catalyst systems. One
major problem involves the separation of the often precious
metal catalyst from the reaction products. Usually, unless
the reaction products can be easily distilled from the
reaction mixture, such as in the Monsanto^ process for
the carbonylation of methanol to acetic acid, the
catalyst-product separation can be a very costly process.
Other disadvantages of homogeneous systems are that they are
generally more corrosive than heterogeneous systems, and the
reaction medium is limited to the solvents in which the
catalyst is soluble.
Immobilization of homogeneous catalysts may not only
combine the advantages of homogeneous and heterogeneous
catalysts but has the potential for some new desirable
features. One feature is site isolation of catalytic
species. This would prevent catalyst site interactions
which are often a mechanism for catalyst deactivation.
There is also the potential for site interaction between
similar or different catalytic sites placed in close
proximity to one another. This could possibly mimic some of
the chemistry demonstrated by enzyme systems.
In this study attention will be focused on the use of
immobilized homogeneous catalysts in the area of carbon


51
monoxide reduction catalysts. Known homogeneous ruthenium
and iridium CO reduction catalysts have been ionically or
covalently attached to inorganic supports. The development
of these catalysts was geared toward discovering catalysts
capable of selectively producing chemicals from mixtures of
CO and gases, referred to as "syngas," under very mild
reaction conditions. The supports chosen were silica gel
and alumina functionalized by various rganos i1anes.
In the course of this study a novel catalytic system
for the selective conversion of syngas and HC1 to
chloromethane was discovered (Equation 1).
h2 + CO + HC1 h2o + ch3ci (1)
This reaction occurs under extremely mild conditions, 25C
and 1 atmosphere pressure, and has the potential to be an
industrially significant process.
Processes involving the conversion of syngas, such as
the Fischer-Tropsch synthesis^ described in Equation 2,
have been known and extensively studied and reviewed since
the early 1900's. ^ ^0 in the last decade concerns over
dwindling petroleum supplies have sparked a renewed interest
CO + H2 catalysts ^ Hydrocarbon Products (2)
(Alkanes, Alkenes, Oxygenates)


52
in the utilization of syngas as a viable source of chemicals
and motor fuels. The Fischer-Tropsch process, which
operates at elevated temperatures and pressures, utilizes a
heterogeneous catalyst usually consisting of one of the
three metals Fe, Co and Ru. The major disadvantage of the
Fischer-Tropsch synthesis which has plagued its development
since its discovery is its inherent lack of selectivity.
51 5 2
Early studies demonstrated that the product
distribution produced by traditional Fischer-Tropsch
catalysts obeys the simple polymerization model below
(Schutz-Flory distribution), Equations 3 and 4. This model
assumes chain growth occurs by incorporation of single
carbon fragments and that the probability of chain growth is
Wn
= n
(1 o<
)2 o< n-1
(3)
=
rP
(4)
rP +
rt
independent of
chain
length.
The term Wn
represents the
weight fraction
of a
certain
carbon number
n,
is defined
as the probability of chain growth and is equal to the rate
of polymerization divided by the sum of the rate of
polymerization and the rate of termination, and (1 <*.)
represents the probability of chain termination.
In order to improve selectivity one needs to deviate
from this type of Schultz Flory kinetics. Recently, there
have been a number of reports'^ of product distributions
deviating significantly from this polymerization model.
Product distributions have been altered by using new metal


53
5 4 5 5
loading techniques, selective catalyst poisoning
(i.e. partial sulfiding) and the use of shape selective
supports such as zeolites.^ ^ Although these reports
look promising, further work needs to be done to establish
whether these effects are experimental artifacts or are due
to actual mechanistic effects.
Due to their potential for greater product selectivity,
homogeneous carbon monoxide reduction catalysts have been a
subject of active research in the last decade. A number of
systems involving primarily cobalt^^0 rhodium^1^2 or
ruthenium^^ have been developed for the production of
mixtures of oxygenated products (i.e. methanol,
methylformate, ethylene glycol) but most operate under
extreme conditions, with pressures usually exceeding 1000
atmospheres.
More recently several homogeneous systems have been
developed which operate under moderate conditions (below
1000 atmospheres). Knifton^ at Texaco reported an active
catalyst for the direct synthesis of ethylene glycol from
syngas at 430 atmospheres and 140-250C. The catalyst
consisted of a number of ruthenium precursors dissolved in a
highly polar molten quaternary phosphonium salt. The active
catalyst species based on IR and NMR studies was
believed to be the anion [HRu^(CO)-^ ] .
Two ruthenium based systems were reported by
£ cn
Dombek0 at Union Carbide. The first involved the
monomer Rh(C0)^, evidenced by high pressure IR and


54
believed to be the active catalytic species for the
conversion of syngas to methanol at 230C and 340
atmospheres pressure. The addition of carboxylic acids was
found to promote the formation of glycol esters.
The second system involved a substantially more active
ruthenium catalyst promoted by ionic iodide promoters and
polar solvents. At 230C and 850 atmospheres H., and CO,
the primary product was free ethylene glycol. The catalyst
precursor, Ru^CCO)^ was thought to be converted to the
two anions [Ru(C0)^I^] and [HRu^(CO)^] by the
reaction below (Equation 5) in a 2:1 ratio which was found
to be the optimum ratio for maximum ethylene glycol
production. The absence of either one of the anions results
in an inactive system.
Ru3(C0)12 + 31- + H2 >2[HRu3(C0)11]' + [Ru(C0)3I3] + 3C0
(5)
In 1977 Muetterties and coworkers^8^^ reported a
novel homogeneous system which converted syngas to light
saturated hydrocarbons under very mild reaction conditions,
180C and 1-2 atmospheres pressure (Equation 6). The
catalyst consisted of the cluster Ir^CCO)^ an a NaCl-AlCl,
Ir4(C0)12
CO + 3H2 >CX to C4 alkanes, (CH3C1) (6)
A1C13-NaCl melt
180C, 1-2 atm
melt solvent and is the first reported homogeneous system
capable of producing non-oxygenated products from syngas.


55
This report was most significant in that it demon
strated the importance of Lewis acid interactions with metal
bound CO, such as demonstrated below, allowing the CO to be
7 0
reduced under mild conditions. Studies by Coliman et al.
M C= 0 A1 Cl5
further substantiated the above finding but also showed that
methylchloride was a reaction product, indicating AlCl^
was being consumed during the reaction.
7 1
A similar system reported by Muetterties and Choi
showed that 0s,(C0)12 in a BBr^ melt was also an active
catalyst for the production of light alkanes under similar
conditions and in this case methylbromide vas detected as a
reaction product.
Methylchloride is an important commodity chemical and
its uses and corresponding consumptions in 1977 are listed
in Table 3-2.
Table 3-2. Consumption of Methyl Chloride 1977.
Uses
Thousands of Metric Tonsa
Methylchlorosilanes
175
Tetramethyl Lead
51
Butyl Rubbers
23
Other
28
Total
277
a Data obtained from "Chemical Economics Handbook"^


56
7 3
The two principal commercial processes for
producing chloromethane are the chlorination of methane and
the methanol-hydrogen chloride process shown below
(Equations 7 and 8). The chlorination of methane process
> 400C
Cl2 + CH4 >CH3C1 + HC1 (7)
> 280C
CH30H + HC1 >CH3C1 (8)
can be accomplished with or without a catalyst. Typical
catalysts for the process are KC1 CuCl, and CuCl^ melts.
Although the primary product of the process is chloromethane
other multichlorinated methanes are produced as well.
Presently, the preferred process is the methanol-HCl route,
which is very selective for chloromethane, up to 97.8%.
Typical catalysts for this process are gamma alumina or
phosphoric acid on activated carbon.
An alternative synthesis reported in 1977 by
7 4
Vannice at Exxon demonstrated that syngas plus a
chloride source, such as Cl or HC1, could be used to
produce chlorinated hydrocarbons at 200 to 1000C and 0.1
to 500 atmospheres pressure. The system consisted of a well
dispersed supported catalyst containing Pt/Re, Pt/Ir, Pt ,
Ir, or Re on an acidic support such as alumina. The
predominant product was methyl chloride but other products


57
such as multichi orinated methanes, ethene, propane and butyl
halides were also produced.
Over the years a large number of supports, both organic
and inorganic, have been utilized to heterogenize transition
metal catalysts. A fairly complete list^ is shown in
Table 3 3.
Table 3-3. Materials Used to Support Metal Complexes.
Inorganic3
Organic3
silica
polystyrene
zeolites
polyamines
glass
silicates
clay
polyvinyls
metal oxide
(i.e. AI2O3,
polyallyls
T i O2 Mg 0)
polybutadiene
polyamino acids
urethanes
acrylic polymers
cellulose
cross-linked dextrans
agarose
3 List obtained from Hartley and Vezey.40
In the work presented here both functionalized silica
gel and alumina supports were used to ionically attach known


58
homogeneous CO hydrogenation catalysts. The choice of these
supports over other available supports was based on their
thermal stability, their intrinsic acidic nature, and the
large variety of silanes (containing functional groups) that
can be bond to the surface ferr metal attachment.
The surface of these supports consists of hydroxyl
groups which can react with silanes of the formula
R^Si(CH2)xB (R=C1, OEt, OMe) by way of the simple
7 5
condensation reaction shown in Equation 9.
5 (OH|3_y
* -0-Si(CH2)xB + 3 ETON (9)
/
)
)H + (OEt)3Si(CH2]xB
)H
The symbol B represents any number of heteroatom groups
(i.e. -PCPh)^, -NH^, -SH) linked to the surface by a
variable length organic chain. The letter Y represents the
number of Si-O-Si bonds to the surface, which is dependent
7 6
on the concentration of organosilane being used. These
attached organosilanes can be used directly or modified to
support transition metal complexes. The B groups used in
the work presented here were -P(Ph).., and -N(CH^)5+I .


59
Experimenta 1
Reagents
All solvents and reagents were used as purchased unless
otherwise stated. Triethoxypropy1 aminos i1ane and
2-(diphenylphospho)ethyltriethoxysilane were purchased from
Petrarch Chemical. Iridium trichloride 3H20, Ir^CCO)^ and
Rh^(CO)-^^ were purchased from Strem. Triruthenium
dodecacarbonyl, Rul_ and [RhClCCO)^^ were purchased
from Alfa. Sodium chloride was dried prior to use in an
oven at 140C.
Hydrogen was purchased from Air Products. Both carbon
monoxide grade C.P. 99.5% and hydrogen chloride technical
grade 99.0% gas were purchased from Matheson.
Silica gel was purchased from W.R. Grace and was
Davison grade #62. Its wide pore diameter was 14 mm, pore
3 2
volume was 1.1 cm /g and had a specific area of 340 m .
Alumina used was Acid, Brockman Activity I, mesh 80-200.
ZnO was purchased from Aldrich.
Ins trumenta tion
All air sensitive manipulations were performed in a
Vacuum Atmosphere Co. model HE-43-2 inert atmosphere box.
Elemental analyses were performed by the Microanalytica1
Laboratory, (C,H and N) University of Florida, Gainesville,


60
Florida, and by Galbraith Laboratories Inc. (Ir and P by
ICP) Knoxville, Tennessee.
GC analyses were performed on two different gas
chromatographs. One was a model 3700 FID/TC Varian gas
chromatograph equipped with a 1/16 inch x 1 meter stainless
steel column packed with Chromosorb P supported diethylene
glycol adipate (DEGA)and a 1/16 inch x 10 foot stainless
steel Poropak Q column. The other was a model 940 FID
Varian gas chromatograph equipped with a 1/16 inch x 8 foot
stainless steel Poropak Q column.
Infrared spectra were recorded on a Perkin Elmer 283B
spectrometer and also on a Nicolet 20DX using diffuse
reflectance (spectra performed by Nicolet).
GC mass spectrometry was performed on a AEI MS30 mass
spectrometer using a KOITOS DS55 data station and equipped
with a PYE Unicam 104 GC containing a 1/4 inch x 5 foot
Poropak Q column. Samples were run by Dr. R. King at the
Microanalytical Laboratory, University of Florida,
Gainesville, Florida.
Fixed Bed Flow Reactor
A specially designed gas flow system was assembled as
shown in Figure 3-1. Hydrogen and carbon monoxide first
enter a Matheson (model 7352) rotometer fitted with No. 610
tubes where the gasses were accurately mixed to the desired
H^CO ratio. When needed, HC1 gas was passed through a
Matheson #601 flow meter where it was combined with the


Figure 3-1. Fixed bed flow reactor.


Bubbler
Septum

Trap
B
S y
IT
Septum
mi < 111
cn
ro
Bubbler C
M2
;H2 gas
:C0 gas
Bubbler D
HCI gas


63
already mixed syngas. The amount of HC1 added was regulated
by teflon needle valve HI. Problems were encountered with
maintaining an even flow of HC1 and a pressure release
bubbler (D) placed before the flow meter proved helpful.
The gasses then were passed through the catalyst bed which
consisted of a powder catalyst packed on top of a glass frit
and held in place with a plug of glass wool. The gasses
leaving the reactor tube were then passed through a
CO^/acetone cold trap and exited finally through a mineral
oil bubbler. The reactor contained two septa for syringing
gas samples for analysis before and after the reactor. The
flow of gasses through the catalyst was regulated by the
teflon needle valve #2. As this valve was closed, a greater
amount of the feed gas was forced through the reactor tube
as opposed to exiting through the mineral oil bubbler (C).
The reactor was designed so that the reactor could be
assembled in an inert atmosphere box. The bypass arm B was
designed for purging the system.
Surrounding the reactor tube was a Lindberg (model
123-8) thermostated tube furnace used to regulate the
reactor temperature. The entire system was made of glass
or teflon tubing due to the corrosive nature of HC1 gas.
Synthesis
Silica Gel Bound Propylaminosilane (silica gel)-^/NNH2
The functionalized support was prepared by a method
7 7
reported by Leyden et al. In a 125 ml Erlenmeyer flask,


64
10 g of silica gel was combined with 50 ml toluene. After
stirring for 10 minutes, 5 ml of triethoxypropylam i nos i1ane
was added. The mixture was stirred for an additional
30 minutes, filtered and the solid was washed with copious
amounts of toluene. The solid was air dried followed by
heating in an oven at 80C for 24 hours. Analysis: C,
3.74%; H, 1.08%; N, 1.40%. (Theoretically represents
1.0 mmole silane per gram silica gel.)
Trimethylammonium Iodide Salt of Silica Gel Bound
Propylaminosilane (silica gelN(CH^)^1
The functionalized support was prepared by a method
7 8
reported by Zombek. In an Erlenmeyer flask equipped
with an addition funnel and blanketed with N?, 10 g of
propylaminosilane bound silica gel, 1.13 g 2,6-lutidine and
80 ml DMF were combined. A solution ( 30 ml) made up of
5.67 g Mel in DMF was added dropwise to the mixture while
stirring. Stirring was continued for 15 hours at ambient
temperature. The reaction mixture was filtered and the
solid washed with acetone and benzene followed by vacuum
drying (0.1 mm Hg) for 24 hours. Analysis, C, 4.52%; H,
1.30%; N, 1.22%; I, 8.37%. (Theoretically represents
.68 mmole trimethylpropylainmonium iodide groups per gram.)
Silica Gel Bound Phosphine Silane (silica g e 1) P ( Ph)-,
The synthetic method was patterned after a preparation
7 9
reported by Schrader and Studer. Silica gel (5.0 g)


65
was dried under vacuum at 32 5 C for 4 hours. In a two
neck 30 ml round bottom flask equipped with a reflux
condenser and a rubber septum in a nitrogen filled glove
bag, the silica gel and 100 ml of 3:1 benzene:p-dioxane
(each distilled from CaH^) were combined. The apparatus
was flushed with N7 for 1/2 hour while vigorously-
stirring. The stirring rate was reduced, 0.45 ml of
2-(diphenylphospho)ethy1triethoxysi 1ane was syringed in and
the mixture was refluxed for 12 hours. After cooling, the
solid was filtered in a glove bag, washed with benzene and
dried under vacuum for 24 hours at 25C.
Silica Gel Bound Phosphine Silane (High Loading)
The same procedure was used as described above for
(silica gel) P(Ph)7 except the amounts of reagents used
were 2 g silica gel, 100 ml 3:1 benzene:p-dioxane and 0.9 ml
2-(diphenylphospho)ethyltriethoxysilane.
Alumina Bound Phosphine Silane (alumina) P(Ph)7
Alumina (10 g Acid Brockman Activity I mesh 80-200) was
washed with dilute HC1 and dried in an oven at 90C for
12 hours. In a 500 ml two neck round bottom flask equipped
with a reflux condenser and a rubber septum, the alumina and
200 ml of xylenes were combined. The mixture was degassed
by bubbling N? through the suspension while stirring for
1.5 hours, followed by syringing in 1.5 ml
2-(diphenylphospho)ethyltriethoxysilane and refluxing for


66
12 hours under After cooling the solid was filtered,
washed with xylenes, toluene, and absolute ethanol followed
by drying at 100C for 24 hours.
[NEt4 ] [Ru3H(C0)11 ]
A procedure was used similar to the synthesis reported
8 0
by Lewis et al. All manipulations were performed in an
inert atmosphere box, or with Schlenk-ware techniques. In
a flask, 0.3291 g Ru3(CO)12, 0.1035 g NaBH4 and 50 ml
tetrahydrofuran (degassed, distilled over CaH2) were
combined. After stirring for 30 minutes the solution
turned deep red. The mixture was filtered through a frit
and the THF was removed under vacuum. The reddish residue
was then combined with 20 ml of degassed methanol followed
by the addition of 0.132 g tetrae thy1ammoniurn bromide
dissolved in 5 ml methanol. The volume was reduced to
10 ml followed by cooling overnight in a C02/acetone
bath. The precipitated solid was filtered, washed with
a small amount of -78C methanol and dried under vacuum
for 24 hours. Analysis: C, 29.38%; H, 3.53%; N,
1.73%. Theoretical: C, 30.75%; H, 2.85%; N, 1.90%.
(Problems were encountered during analysis due to 0^
sensitivity.)


67
[Cs][Ru(CO)3)3]
A procedure was used similar to that reported by
81
Griffith and Cleare. In a 100 ml round bottom flask
equipped with a reflux condenser, 1.1 g anhydrous Rul^,
8.3 ml hydroiodic acid and 8.3 ml formic acid were
combined. The mixture was refluxed and stirred for 12
hours. After cooling, the mixture was filtered and 0.83 g
CsCl was added to the filtrate. The solvent was removed on
a rotary evaporator, the residue was extracted with absolute
ethanol and the solvent was then removed again. Analysis:
C, 4.2%; I, 54.8%. Theoretical: C, 6.2%; I, 54.5%. The
brownish- yellow residue was recrystallized in absolute
ethanol.
Silica Gel Functionalized [1^13(00)3] and [ HRu3( CO ) ^ ]J "
In a 50 ml Erlenmeyer flask 0.1136 g of the ammonium
iodide salt of silica gel bound propy1 ami nosilane (8.37% I),
0.0222 g Cs[RuIj(CO)j] and 20 ml of tetrahydrofuran were
combined. The purple mixture was heated while stirring and
remained at reflux temperature for 10 minutes. After
cooling, the light maroon solid was filtered and washed with
THF. The resulting solid was brought into an inert
atmosphere box and combined with an intensely maroon colored
solution consisting of[NEt^][HRuCO)^^ ] dissolved in
5 ml of THF. After the mixture was stirred for 10 minutes,


68
the light maroon colored solid was filtered, washed with THF
and dried under vacuum at 25C.
Ir(C0)2Cl(p-toluidine)
8 2
A procedure reported by Klabunde ^ was used. In a
100 ml round bottom flask equipped with a reflux condenser
and a gas dispersion tube, 1.015 g IrCl,*3H?0, 0.290 g
anhydrous LiCl, 40ml 2-methoxyethano1 and 4.5 ml H?0 were
combined. The apparatus was purged with through the
gas dispersion tube for 15 minutes. The was switched
to CO and a slow bubble rate was maintained while refluxing
and stirring for 10 hours. The mixture was cooled and while
purging with N^, 0.377 g of p-toluidine was quickly
added. The mixture was stirred for 15 minutes and added to
145 ml of H^O. The purple precipitate was filtered in
air, washed with 90 ml 0 and dried under vacuum for 1
hour. The solution was filtered followed by removal of the
solvent under vacuum. Analysis: C, 30.12%; H, 2.53%; N,
3.90%; Theoretical: C, 27.92%; H, 2.24%; N, 3.35%.
(Silica Gel)\/\ P(Ph) 2Ir4(CO) n
The method used was derived from a preparation reported
7 9
by Schrader and Studer. In an inert atmosphere box in
a 500 ml Parr pressure bottle set-up (described in the
experimental section of Part Three) a degassed solution of
76.5 ml 2-methoxyethanol and 2.7 ml H^O was combined with


69
0.055 g Ir(CO)0C1(p-toluidine) 18 g mossy zinc (acid
washed and chopped into small chunks) and the entire yield
of the resin resulting from the preparation of silica gel
ound phosphine silane ( 5 g). The system was pressurized to
40 psi ten times with argon followed by ten times with CO.
While stirring, the system was pressurized to 55 psi with CO
and heated to 90C. (Note: Good stirring was essential to
obtain an active catalyst. A 1/2 inch star stir bar,
purchased from Fisher Chemical Co., worked well.) After 24
hours the system was cooled and the slurry was decanted from
the mossy zinc in air, followed by filtering. The yellowish
support was washed with THF and dried under vacuum for 24
hours at 25C. (Heating while drying may result in
decomposition of the supported carbonyl cluster.) Analysis:
Ir, 0.23% (obtained by ICP).
(Silica Gel )-^^ P(Ph) 2lr4(CO) (High Loading)
The same procedure was used as above for
(silica gel) P (Ph) 21 r^ ( CO )^-^ except the pressure bottle
set-up was loaded with 0.110 g Ir(CO)2Cl(p-toluidine),
153 ml 2-methoxyethanol, 5.4 ml H^O, 36 g mossy zinc and
the entire yield from the preparation of high loading silica
gel bound phosphine silane. Analysis: Ir, 0.69%.


70
(Alumina )P( Ph) £l r 4( CO ) i \
The same procedure was used as above for
(silica gel P (Ph) ^ I r^ ( CO )^ ^ except the reagents
loaded in the pressure bottle set-up were: 3 g alumina bound
phosphine silane, 0.056 g Ir(CO)^C1(p-toluidine), 76.5 ml
2-inethoxyethanol 2.7 ml H^O and 18.0 g mossy zinc.
Analysis: Ir, 0.75%: P, 0.84%. (The theoretical Ir^ : P
ratio is 1:27.)
Ir4(CO)i2 on Silica Gel (Physically adsorbed, 2.5% Ir)
The method used was derived from a preparation reported
8 3
by Howe. In a 100 ml round bottom flask, 2.0 g silica
gel (untreated), 0.072 g Ir^(C0)^2 and 50 ml cyclohexane
were combined. After stirring for 3 hours the solvent was
removed under vacuum and the resulting solid was dried for 6
hours at 25C.
Ir4(CO)11P(Ph)3
The synthesis was derived from a preparation reported
84
by Shapley and Stuntz. In a 250 ml Parr pressure bottle
1 ml H^O was combined with 30 ml 2-methoxyethanol. Carbon
monoxide was bubbled through the solution for 15 minutes by
way of a syringe needle. Quickly, 0.155 g (0.397 mmole) of
Ir(CO)2Cl(p-toluidine), 0.026 g (0.99 mmole) P(Ph)^,
3.0 g mossy zinc (acid washed) and a stir bar were added. A
pressure head was placed on the bottle and the system was


71
purged with 60 psi CO ten times. Under 60 psi CO, the
mixture was heated while stirring to 90C. After 30
minutes the mixture was cooled, the pressure released and
the mixture filtered. The yellow filtrate was evaporated to
dryness under vacuum.
The residue was dissolved in 50 ml of 5:1
hexanes:methylene chloride solution and added in portions to
a 14" long, 1/2" diameter column packed with 230-400 mesh
silica gel. The yellow solution separated into two yellow
bands upon elution with 5:1 hexanes:methylene chloride.
Each band was collected and the solvent was removed under
vacuum. The first band off the column yielded a yellow
crystalline solid, Ir^(CO)^(Ph)^, and the second
band yielded a yellow oil IrCO)^Q(P(Ph)^^.
Infrared analysis of both compounds matched well with
4 8
literature reported spectra.
(OEt)3Si(CH2)2P(Ph)2Ir4(CO)n and
[(OEt)3Si(CH2)2]2lr4^CO)Mixture
The preparation used was reported by Schrader and
7 9
Studer. In an inert atmosphere box in a 500 ml Parr
pressure bottle, a degassed solution consisting of
100 ml 2-methoxyethanol and 3.2 ml 0, 0.20 g
IrCl(CO)^(p-toluidine ) and 4.5 g mossy zinc (acid
washed) were combined. A pressure head was placed on the
bottle and it was purged with 40 psi ten times with argon
followed by ten times with CO. Under 55 psi of CO the


72
system was heated to 90C while stirring. After 12
hours the mixture was cooled, brought into an inert
atmosphere box and filtered. The solvent was removed from
the filtrate under vacuum. The IR spectrum of the
resulting yellow residue showed characteristic IR bands
for both iridium silane complexes. No separation was
attempted.
(Alumina) \A P ( Ph) 2 I r Cl ( CO) P ( Ph)3
The procedure used was derived from a preparation
8 5
reported by Evans et al. In a 100 ml round bottom
flask, 0.11 g of I r (CO) Cl (P( Ph) 1.0 g alumina bound
phosphine silane and 55 ml benzene (dried over CaH-, and
distilled) were combined. After the mixture was stirred at
ambient temperature for 72 hours under the support was
filtered, washed with benzene and dried under vacuum.
IrCl(CO)(P(PIO3)2 on Alumina (Physically adsorbed)
In a 100 ml round bottom flask, 0.11 g Ir(CO)Cl(P(Ph)^)^,
2.0 g alumina (acid washed) and 50 ml benzene were combined.
After stirring at ambient temperature for 120 hours under
, the solvent was removed by vacuum. The support was then
dried under vacuum for 12 hours.


73
Pyrolyzed RhftCCO)]^ on ZnO (0.6% Rh)
The preparation used was reported by Ichikawa.^^ In
a 300 ml round bottom flask, 0.042 g Rh^CCO)^^, 4.0 g
ZnO and 200 ml acetone were combined. The mixture was
stirred under for 24 hours and then the solvent was
removed under vacuum. The resulting solid was placed in a
glass tube and heated to 160C under vacuum for 2.5 hours.
Results and Discussion
Polymer Supported [Ru(CO)3I3]" and [HRujC CO ) \ \ ] ~
Synthesis and characterization
The support used to attach the ruthenium anions
[Ru(C0)^Ij]~ and [HRu^(CO)^^] was an ami nopropylsi1 ane
functionalized silica gel*' that had been modified to a
7 8
trimethylpropylammonium iodide form. The synthetic
procedure for this support is shown in Figure 3-2.
Having a sufficient concentration of quaternary
ammonium iodide groups on the silica gel surface was an
important consideration. This would allow the ruthenium
anions to interact with one another once ion exchanged onto
the support. The ruthenium anion interactions are suspected
6 7
to be important because in Dombek's0 homogeneous system
both anions had to be present in solution for catalysis and
neither anion was a good CO reduction catalyst.


Figure 3-2. Synthetic route for the preparation of
trimethylpropylammonium iodide functionalized
silica gel.


75
Step 1
j
i OH + (OEt)3Si-^s/>NH2 Toluene .
Step 2
\
O-Si^v^NH
/
2
+
CH31
DMF
\
O Si-^V^NHo
/

o-Si^v^n(ch3)3i


76
Based on an infrared study, Nyberg and Drago
8 7
reported that the concentration of organosulfide groups
needed on a silica gel support to allow the formation of the
rhodium carbonyl dimer shown below was 0.20 mmole S per gram
of silica gel.
Elemental analysis of the quaternary ammonium iodide
modified support showed that the support contained 8.37%
iodine which translates theoretically to 0.63 mmole
quaternary ammonium iodide groups per gram of silica gel.
Thus the concentration of quaternary ammomium iodide sites
should be more than sufficient to allow site interaction.
The anions [Ru(C0)jI^]" and [HRu^(C0)^]
were first synthesized separately as shown by Equations 10
and 11, and isolated as the cesium and tetraethylammonium
salts respectively.
CsCl
RuI 3 + HI + HC00H > >Cs [Ru(CO ) 3I 3 ]
reflux
(10)
THF [NEt4]Br
Ru3(C0)12 + Na [ BH4 ] >
*[NEt4][HRu3(C0)n] (11)
2 5C


77
A successful method for ion exchanging the two
ruthenium anions onto the support utilized two separate ion
exchange reactions in tetrahydrofuran. In the first ion
exchange reaction, the modified silica gel support was
stirred in a Cs[Ru(C0)-I^] THF solution which contained
a quantity of [Ru(CO)^I^] ions equal to one half the
number of theoretically available quaternary ammonium iodide
sites. The infrared spectrum of the isolated support after
stirring for 10 minutes at 25C showed no evidence of
[ Ru( CO I-. ] being present (Figure 3-3b). Stirring
the support for 15 minutes under reflux conditions resulted
in an infrared spectrum (Figure 3-3c) containing two fairly
intense bands at 2091 and 2021 cm ^ (Table 3-4). These
correspond well with the CO stretching bands observed at
2100 and 2027 cm ^ for the KBr spectrum of Cs[Ru(COI^]
(Figure 3-4a). (The 2027 cm ^ value is the average
frequency of the two close bands at 2033 and 2021 cm ).
The resulting [Ru(C0)^I,]~ exchanged support was then
contacted with degassed, intensely maroon colored THF
solution containing the dissolved salt [NEt^][HRu^(CO )^^].
After 10 minutes of stirring at 25C the isolated support
contained three main infrared bands (Figure 3-4c) in the CO
stretching frequency; 2099, 2036 and 1987 cm ^. These
infrared bands correspond well with what would result from
adding together the two spectra of the separate anions. The
infrared result fairly conclusively shows that the modified
silica gel support contains both the anions [Ru(C0)^I^]


Figure 3-3. Infrared spectra in the range 2500-2600 cm"l
of a) (silica gel)N(CH3)3 I, (nujol mull);
b) [Rul3(C0)3]_ exchanged at 25C, (nujol
mull); c) [RuI3(CO)3]" exchanged at reflux
temperature, (nujol mull).


79
CM 1
2500
I
2000
I
1800
I
1600


Table 3-4. Comparison of Infrared Carbonyl Stretching Frequencies of
Supported and Non-Supported Ruthenium Complexes.
Compound Environment
V C = 0 (cm-1)
1)
Cs [Rul3 C CO )3 ]
KBr
210 0(s) 2033(S) 2021(g)
2)
[NEt4][HRu(C0)n]
CH3CN
2070(w), 2010(g), 1998(g), 1440(m)
[2075(vw), 2018(vs), 1985(g), 194S(m)]
3)
[RUI3 ( CO )3 ] on
nu j ol
2091(vs), 2021(g)
(Silica Gel )^N(CH3) 3 +
4)
[RuI3(C0)3]-+[HRu3(C0)n]-
nu j ol
2099(g) 2036(Br) 1987(Br)
on (Silica Ge 1N(CH3)3 +
a Johnson et al.^0


Figure 3-4. Infrared spectra in the range 2500-1800 cm'1
of a) Cs [R.UI3 ( CO K ] (KBr);
b) [NE14] [HRujCCOJn] (in CH3CN);
c) [Rui3CO)3]" and [HRujCCO)i\] '
on (silica gel )/\^ N ( CH 3) 3+ (nujol mull).


82
2500 2000 1800
CM-


83
and [HRu^CCO)^] but the relative concentration of
each is unknown .
Catalysis
Approximately 0.5 grams of the ruthenium substituted support
was placed in a reactor tube in an inert atmosphere box, and the
tube was then placed in the flow reactor system described in the
experimental section. On passing a 3:1 H^rCO mixture through
the catalyst at atmospheric pressure and a flow rate of 10
cm'Vminute no products were observed at temperatures below
150C. At 150C a small amount of methane was detected along
with some C 0 ^, which is often produced as a byproduct of
methanation or Fischer-Tropsch by way of the water gas shift
reaction. On raising the temperature to 175C there was little
or no increase in methane production.
Covalently Supported Ir4(C0)n
Synthesis
The method used to attach Ir^(CO)x (where x = 10
or 11) clusters onto the surface of silica gel or
alumina involved covalently bonding them to surface
bound phosphine silane groups. The synthetic procedure
used was derived from work published by Schrader and
79
Studer and is shown in Figure 3-5. The silane,
2-(diphenylphosphino)ethyltriethoxysilane was first bound to
the surface of the support by reaction of the ethoxy groups
on the silane with the hydroxyl groups on the support


Figure 3-
Synthetic route for the preparation of (silica
gel or aluminaNAP(Ph)2lr4(C0)ix-


85
Step 1
H 4- (OEt)3Si
P(Ph),
Benzene
D i oxane
2 Reflux
)-Si^S^P(Ph} + 3 ETOH
/ 2
Step 2
CO
IrfCQ) Cl (p-toluidine) >
2 h2o
2-methoxyethanol
11


86
surface. The next step involved assembling the tetrairidium
clusters from the monomer Ir(CO)^C1(p-toluidine) during
covalent attachment to the surface bound phosphine groups.
Through a fairly extensive FTIR study of the metal loaded
7 9
silica gel Studer and Schrader demonstrated that the
primary species functionalized on the surface was a mixture
of the following two clusters, ~PIr4(C0)^1 and
P2Ir4(CO)10-
It was found that complete mixing in the cluster
supporting step was an important factor in obtaining an
active catalyst. Attempts to double the synthesis procedure
(using 10 g of support) resulted in severe stirring problems
and thus an inactive catalyst.
The three primary catalyst formulations investigated in
this study are shown in Table 3-5 along with their elemental
analyses.
Infrared characterization
A fairly extensive Fourier transform infrared study was
7 9
conducted by Studer and Schrader on tetrairidium
clusters bound by 2-(diphenylphospho)ethy11riethoxysi 1ane
functionalized silica gel. The characteristic carbonyl
stretching bands reported for both the mono-phosphine
substituted (silica ge 1)P(Ph)?Ir^(CO)^ and the
diphosphine substituted (silica ge 1)(x/N P(Ph)^1r4^CO)^q
are listed in Table 3-6. Also included is a summary of


87
Table 3-5. Elemental Analysis of the Primary Catalyst
Formulations.
Catalyst Wt%
Ir P H C
1. (Silica Gel) Va P(Ph)2Ir4(C0)n
.23
2. (Silica Gel)\/'P(Ph)2Ir4(C0)11
.69 6.40 1.34
3. (Alumina) Va P(Ph)2Ir4(C0)n
.75 .84


Table 3-6. Infrared Spectra of Silica Gel or Alumina Bound Tetrairidium Clusters
and Molecular Analogs.
Compound Environment yCO (cm-*-)
Cyclohexane 2082^, 2048s, 2013m
1869y^, 1 8 5 3 jvj, 1 8 2 9 ¡vj
Ir4(C0)11P(Ph)3
Ir4(C0)nP(Ph)3 a
Ir4(C0)nP(Ph)3 on Alumina
(Silica)vAp(Ph)2Ir4(CO)11 a
(Silica)(s/NP(Ph)2)2Ir4(CO)10 a
( Alumina) (n/^ P(Ph)2)i>(2)Ir4(CO)n>(io)
(Silica) (Va" P(Ph) 2) i f (2 )Ir 4(C0) n ( (10)
ch2ci2
2 08 8M) 2056Vs, 2 0 20s
18 87y\i/, 1 84 7m, 1 8 2 5m
Nu j ol
2083w, 2 0 51s, 2019m
Wafer
2090p|, 2 06 ljvj, 202 3m
1890yw, 1 8 25jvj, 1 83 5m
Wafer
2 074s, 2050vs, 2 017M
Diffuse
Reflectance
211 4M 2060m, 2004s
Nu j ol
2092sh> 2070Shj 2041s, 2005m
a Schrader and Studer.7^


89
spectra taken of the polymer bound tetrairidium clusters and
molecular analogs used in this study.
The majority of the spectra were taken on a Perkin
Elmer 283B grating spectrometer except for the spectra of
Ir^(C0)x (x=10 or 11) bound to phosphine functionalized
alumina. These spectra were done by Nicolet on a Nicolet
20DX FT infrared spectrometer, using the diffuse reflectance
technique.
Spectra obtained for silica gel bound tetrairidium
clusters at two different iridium concentrations, 0.23% and
0.69%, are shown in Figure 3-6. At the low iridium
concentration (0.23%) the carbonyl stretching frequencies
due to the tetrairidium cluster were almost
indistinguishable from the background. The infrared
spectrum of the 0.69% Ir support showed more pronounced
carbonyl stretching bands. However accurate measurement of
these bands was difficult due to the limitations of the IR
spectrometer. Therefore it was difficult to determine if
the tetrairidium cluster was mono or diphosphine
substituted.
The spectra taken on the analogous alumina system
(Ir = 0.75%) were more conclusive. Figure 3-7 (a,b) shows
the FTIR spectra of the phosphine silane supported alumina
and metal supported phosphine silane functionalized
alumina. The spectrum resulting from the subtraction of
spectrum (a) from (b) is shown in (c). The remaining three
bands, 2114, 2060 and 2004 cm ^ of the tetrairidium


Figure 3-6. Infrared spectra (nujol mulls) in the range
2500-1600 cm-1 of (silica gel)vAP(Ph)2Ir4(C0)n
a) 0.23% Ir; b) 0.69% Ir.


91
CM-1


Full Text
ACTIVATION OF HYDROGEN AND
BY TRANSITION METAL
CARBON MONOXIDE
COMPLEXES
By
JAMES G. MILLER
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

To my parents, Mary and George Miller, and my wife,
Nan, whose constant support and encouragement made this
work possible.

ACKNOWLEDGEMENTS
I wish to express my deep appreciation to my research
director, Professor Russell S. Drago, for his guidance,
motivation, and understanding during my years at the
University of Illinois and the University of Florida.
A very grateful thank you goes to Professor Glenn C.
Vogel for his encouragement and friendship.
I would like to thank the members of the Drago research
group, both past and present, for their help, discussions
and friendship. Among the group Mike Desmond, Dean Oester,
Pete Doan, Jim Stahlbush and especially Keith Weiss deserve
special thanks. Robert King and Chris Schiriner are
acknowledged for their invaluable assistance with the GC
mass spectrometry and electrochemistry studies,
respectively.
Financial support by the University of Illinois, the
University of Florida and Professor Drago in the form of
teaching and research assistantships is gratefully
acknowledged.
Finally, a very special thanks go to Ginger Solano and
my wife Nan for their patience and help in preparing this
manuscript.
i i i

TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iii
ABSTRACT vi
CHAPTER
I. INTRODUCTION 1
II. ACTIVATION OF MOLECULAR HYDROGEN 4
Introduction 4
Experimental 11
Materials 11
Instrumentation 12
Synthesis 13
Thermodynamic Measurements 14
Hydrogen Gas Flow System 15
Results and Discussion 24
Conclusion 46
III. IMMOBILIZED HOMOGENEOUS CARBON MONOXIDE
REDUCTION CATALYSTS 48
Introduction 48
Experimental 59
Reagents 59
Instrumentation 59
Fixed Bed Flow Reactor 60
Synthesis 63
Results and Discussion 73
Polymer Supported [RuCCO)3I3]“ and
[HRu3 (C0)lx ]- 73
Synthesis and characterization 73
Catalysis 83
Covalently Supported Ir4(C0)]_]_ 83
Synthesis 83
Infrared characterization 86
Catalysis 94
CH3CI catalyst development 102
IV

Halogen sources 126
GC Mass spectrometry 131
Mechanism 142
Conclusion 146
IV. IMIDAZOLE FUNCTIONALIZED SILICA GEL 149
Introduction 149
Experimental 153
Materials 153
Instrumentation 153
Synthesis 154
Results and Discussion 158
Synthesis - Imidazole Support 158
Hydroformylation 167
Conclusion 169
V. SOLUBLE BIMETALLIC COMPLEXES 171
Introduction 171
Experimental 173
Materials 173
Instrumentation 173
Synthesis 177
Results and Discussion 181
Ligand Preparation 181
Metalomers, Synthesis and Characterization . 182
Electrochemistry 195
Conclusion 199
VI. SUMMARY AND CONCLUSION 201
REFERENCES 203
BIOGRAPHICAL SKETCH 211
v

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
ACTIVATION OF HYDROGEN AND CARBON MONOXIDE
BY TRANSITION METAL COMPLEXES
By
James G. Miller
December 1985
Chairman: Russell S. Drago
Major Department: Chemistry
Reported here are four studies related to the catalytic
processes involving the activation of carbon monoxide and/or
molecular hydrogen by transition metal complexes. The first
study investigates the process of hydrogen activation by
square-planar rhodium (I) complexes of the formula
(P(p-tolyl)^RhClB where B is P(p-tolyl)^,
tetrahydrothiophene (THTP), pyridine and N-methylimidazole .
Enthalpies were determined for the reaction of the
P(p-tolyl)^ and THTP complexes with H? forming cis
dihydride complexes of the formula (P(p-toly1)^)^RhClBH^.
Attempts to determine enthalpies for the pyridine and
N-methylimidazole complexes were unsuccessful.
The metal-hydrogen dissociation energies determined
from these enthalpies were found to be insensitive to the
ligand variation around the rhodium center.
In the second study, ruthenium and iridium homogeneous
CO reduction catalysts were immobilized on silica gel and
alumina. Ionic attachment of the two ruthenium anions
vi

[Ru(CO)^Ij] and [HRu,(CO^] to ammonium
iodide functionalized silica gel, as demonstrated by
infrared showed no syngas (CO and H ^) conversion up to
175°C and 1 atm pressure.
A physical mixture of AlCl^ and Ir^(CO)^
covalently attached to a phosphine silane functionalized
silica gel or alumina was found to selectively produce
CH^Cl from syngas under very mild conditions, 25°C, 1
atm pressure. Replacement of AlCl^ as the chloride source
by addition of HCl(g) to the syngas feed enabled production
of C1LC1 with 99% selectively at temperatures up to
100°C. The novel chemistry was demonstrated with other
halogen sources: aqueous HC1, Cl^ and HBr (producing
CH,Br). The presence of a Lewis acid and the phosphine
silane linkage appeared to be important for their catalytic
properties.
In the third study a 4(5) substituted imidazole
functionalized silica gel support was synthesized to
heterogenize a homogeneous rhodium imidazole
hydroformylation catalyst. The synthesis utilizes Schiff
base reactions between an aminosilane functionalized silica
gel, histamine and 1,4-dihydroxy-2,5-dibenzaldehyde. The
rhodium metalated support was active for the conversion of
1-hexene but suffered severe metal leaching.
In the fourth study a series of soluble bimetallic
complexes of the formula [M(11)(DIOX)BF2] , (M = Cu, Ni,
Zn, Pd; DIOX = bis-4 - tert-buty1-2,6-diformy1-pheno1 dioxime)
vii

was synthesized and characterized. These complexes are
formed from analogous insoluble 0-H”**0 bridged complexes by
reaction with BF^Et^O. Electrochemical studies were
performed on the Cu(II) BF^ capped complex in acetone and
DMF and illustrated strong metal site interactions.
viii

I. INTRODUCTION
The field of catalysis is one of the most active and
intensely pursued areas of chemistry research. The
overriding goal of this research, driven primarily by
its economic importance, is to develop better and more
efficient catalysts.
Reported here are the results of four studies all
related to catalytic processes (i.e. hydrogenation, carbon
monoxide reduction, hydroformylation) involving the
activation of carbon monoxide and/or molecular hydrogen by
transition metal complexes. These studies focus on two
different aspects of catalysis research: 1) gaining an
understanding of chemical transformations taking place in a
catalytic cycle and 2) developing new and novel transition
metal catalysts. In the first study thermodynamic data
were obtained on the activation of molecular hydrogen by
square-planar rhodium(I) complexes of the formula
[P(p-tolyl) ]2RhClB (B = P(p-tolyl)3, THTP, Py, Helm).
These results provide needed information on the strength of
the metal hydrogen bonds formed upon activation of molecular
hydrogen by a typical hydrogenation catalyst, "Wilkinson's"
catalyst'*’ and the sensitivity of these bonds to variation
in the ligand environment around the metal center. These
1

2
results also give insight into adverse effects of additives
such a pyridine to the catalytic system.
In the second study immobilized homogeneous transition
metal catalysts were synthesized and tested for their use in
developing selective carbon monoxide reduction catalysts
which operate under mild reaction conditions. A low
pressure and temperature catalytic system was discovered and
described for the conversion of syngas (CO + H^) and HC1
selectively to chloromethane using a bifunctional supported
iridium cluster catalyst. The active catalyst precursor
consists of Ir^CCO)^ covalently attached to a phosphine
silane functionalized silica gel or alumina and can be
operated in the presence or absence of an MCI-
co-catalyst.
The third study, which relates very closely to the
immobilized catalysts used in the previous study, involves
the development of a 4(5) substituted imidazole
functionalized silica gel support. The new support was
designed to heterogenize a reported homogeneous rhodium
imidazole hydroformylation catalyst of the formula
2 3
[Rh(imidazole)],. ’ The synthesis and characterization
of this new support are reported along with preliminary
tests on the hydroformy1 ation activity of the rhodium metal
loaded support.
The fourth and final study reported deals primarily
with the synthesis and characterization of new soluble
bimetallic macromolecules which might be capable of

3
facilitating bifunctional catalysis similar to that
demonstrated in the second study. These complexes
synthesized are of the formula [M(DIOX)BF^^ (DIOX =
bis-4-tert-butyl-2,6-dif orinyl-phenol dioxirne and M = Cu , Ni ,
Zn, Pd) and contain two metal centers in close proximity
allowing metal site interactions.

II. ACTIVATION OF MOLECULAR HYDROGEN
Introduction
Activation of molecular hydrogen by metals is an
important fundamental process with relevance to many
catalytic systems (i.e. hydrogenation of olefins,4
hydroformylation,^ and reduction of carbon monoxide by
H^) and to storage of by dissolution in metals.
In order to develop better and more efficient
catalysts, it is important to determine what metal hydrogen
bond dissociation energies are needed to affect desired
chemical transformations. For example, a transition metal
hydride complex will not be a good hydrogenation catalyst if
its M-H bond strengths are so large that it is unable to
easily transfer hydrogens to an olefin.
To date, very little thermodynamic data have been
reported in the literature regarding metal hydrogen bond
dissociation energies and their dependence on various
ligands in the metal coordination sphere. The reaction of a
series of square planar rhodium (I) complexes of the formula
[P(p-tolyl)3]2RhClB (B=P(p-tolyl)3, THTP, Py, Melm)
with molecular hydrogen forming six coordinate rhodium
(III) dihydride complexes (Equation 1) provided an excellent
opportunity for this type of study.
4

5
[P(p-tolyl)3 ]2RhClB + H2< ¿ [ P ( p - toly 1), ] 2 RhCl B (H, ) (1)
The complex [P(p-tolyl)3]2RhClB, (where B=P(p-toly1)^)
often termed "Wilkinson's catalyst," has been extensively
studied since it was first reported to be a good
hydrogenation catalyst by Wilkinson et al.1 in 1966. To
this date, a number of studies and mechanistic schemes have
8 _ i 2
been published. The most recent was proposed by
13 14
Halpern et al. * and is shown Figure 2-1 where
L = P(p-tolyl) 3 or PCC^H^)^, S = solvent, and C = Cn
represents some non-sterically hindered unconjugated olefin.
In concentrations of up to 0.1M excess phosphine the
predominant catalytic pathway is not through direct
hydrogenation of RhClL^ I but through a dissociative
pathway where RhClL^ dissociates a phosphine generating
the unsaturated three coordinate species RhClL^ II. This
was found to activate H2 1 04 times faster than RhClL^
generating another coordinately unsaturated complex
RhClL3(H)2 III which then reacts with an olefin giving
the six coordinate complex IV. Stepwise hydrogen transfer
to the olefin produces the alkane product and also
regenerates the three coordinate complex II. The catalytic
cycle then continues along the pathway contained in the
dotted circle.
A number of studies have been published attempting to
correlate changes in the ligand environment around the

Figure 2-1. Mechanistic scheme proposed for the
hydrogenation olefins by "Wilkinson1
Catalyst."

7
L L
Rh
C,^
I
S
-L
\ /
-c—c-
H
l v
Rh
Cl^ I
:c=c:
H
L S
Rh
Cl^
IT
.c=c.
L V H
^ 1 ^
Rh
Cl^ ^ L
S
nr

8
rhodium center to catalytic activity. Most of these studies
involved changing all three phosphines with other phosphines
and other 2 electron donating bases. When a series
of para-substituted aryl phosphines were used, it was found
that catalytic activity increased as the electron donating
ability of the phosphine increased. This could be due to
the more electron donating phosphines making the rhodium
more basic improving its ability to activate H-, (as well
as to back bond into olefins).
When alkyl phosphines were used, which are even more
electron donating than aryl phosphines, catalytic activity
was diminished. These results can be interpreted in a
number of ways. First, the alkyl phosphines could be making
the rhodium center so basic that the rhodium hydride and
rhodium olefin complex are becoming too stable. Second,
steric factors may also be playing an important role. The
less bulky more electron donating phosphines may be binding
too tightly to the rhodium center preventing the necessary
phosphine dissociation steps that provide important
coordinative unsaturation. When the bulky aryl phosphines
19
were used, crowding around the metal center may be
increasing the tendency for ligand dissociation.
Further studies have used N, S, As and Sb
donors^’^’^’^^ around the rhodium center. Also, it was
reported1 that large excesses of pyridine, acetonitrile
and various sulfur donors added to solutions of
RhCl ( P ( C^H;- ) j j greatly reduce catalytic activity.

9
Due to the complexities of a catalytic system it is
difficult to predict exactly what reactions are being
affected by variations imposed on the system unless each
catalytic reaction step can be studied separately. This
study will hopefully give some insight into one segment of
the catalytic reaction, that is the effects of ligand
variation on the activation of molecular hydrogen by rhodium
complexes with structures similar to Wilkinson's.
A convenient and fairly simple method for making
derivatives with one ligand around the rhodium center of
Wilkinson's catalyst being varied was found making use of
the dimer bridge cleavage reaction shown in Equation 2.
2 2 2 3
Calorimetric studies on this ’
P Cl P B
\ / \ / \ /
Rh Rh + 2B < » 2 Rh (2 )
/ \ / \ / \
P Cl P P Cl
(P = P(p-tolyl)3)
and two other chloro bridged dimer systems [RhCl(CO)?^4
2 5
and [RhCl(COD)^have previously been reported by
the Drago research group.
The bridge cleavage reaction of the phosphine dimer
([RhC1(P(p-toly1),)^]2) was found to occur with nitrogen,
phosphorus and sulfur donors. Attempts using oxygen donors
were unsuccessful. By way of and ^P NMR the
geometric structure of all the monomeric base adducts formed
were found to be the same; that is the base occupied a

10
position cis to the chlorine, as shown in Equation 2. Heats
obtained for the bridge cleavage reaction were incorporated
2 ó 2 7
into the E, C and W correlation ’ (Equation 3) and E^
and parameters were generated for the three coordinate
acid (P(p-tolyl)j)2RhCl.
- AH = EaEb + CA CB + W (3)
The monomeric base adducts generated in solution were
also shown to react with molecular hydrogen at ambient
temperature and pressure (Equation 1). The six coordinate
rhodium (III) dihydride complexes formed (shown below) were
found to have the same geometric structure, again using ^H
and NMR. The two inequivalent hydrides end up cis to
H
Cl
x x.
H
each other and the two equivalent phosphines occupy trans
pos itions.
This study deals specifically with the thermodynamic
aspects of the activation of molecular hydrogen by
Wilkinson's catalyst and its derivatives. Determination of

11
theAH for Equation 1 will provide us with a better
understanding of the influence of donor strength on the
activation of molecular hydrogen and on the average Rh-H
bond strength.
In addition, the resulting thermodynamic data could
possibly be entered into the E, C and W correlation and E^
and parameters could be determined for the five
coordinate acid "(P(p-tolyl)^2RhCl(H)2." By comparing
these E and C parameters to the E and C parameters of the
three coordinate acid "(P(p-tolyl)^RhCl," the effect of
oxidative addition of H? on the acidity of the rhodium
center could be quantitatively determined.
Experimental
Materials
Toluene was dried and degassed by first refluxing over
CaH^ for 24 hours, collected by distillation under
and then subjected to freeze pump thawing (a minimum of 5
cycles using a mercury diffusion pump). It was then stored
in an inert atmosphere box until needed. Rhodium
trichloride • 31^0 was purchased and used without further
purification.
All bases used in this study were purchased and
purified by the following methods. Tri-p-tolylphosphine was
recrystallized in hot absolute ethanol followed by drying

12
under vacuum. Pyridine (Py) was stored over KOH pellets
overnight, then distilled from BaO under (middle
fraction taken, boiling range 112.0 - 112.5°C).
Tetrahydrothiophene (THTP) was fractionally distilled over
CaH^ at atmospheric pressure. N-methylimidazole was
fractionally distilled over CaH^ at 10 mmHg pressure and
the middle fraction taken. Dimethylthioformamide was dried
over 4A molecular sieves. All liquid bases were degassed by
freeze pump thawing.
Ethylene, hydrogen and nitrogen gases used were
obtained from Linde (Union Carbide); the hydrogen and
nitrogen were of ultra-high purity ( 2 ppm 0^, 3 ppm
moisture).
High capacity oxygen traps were purchased from L.C.
Company, Inc. These were designed to remove 0¿ to below
0.1 ppm with a gas flow of less than 3 liters per minute.
The traps contain a Mo based indicator which is blue-green
when activated and grey when spent. The traps were
periodically regenerated by placing them in a Lindberg
(model 123-8) tube furnace at 375°C while passing Hgas
through them at a rate of 30 cc/min for 20 minutes.
Instrumentation
All air sensitive manipulations were performed in a
Vacuum Atmosphere Co. model HE-43-2 inert atmosphere box,
in specially designed Schlenck-ware glassware. Elemental

13
analysis was performed by the Microanalytical Laboratory,
University of Illinois, Urbana, Illinois.
Electronic absorption spectra were taken on a Cary
14-RI spectrometer equipped with a Varian constant
temperature chamber in the sample compartment. The chamber
was coupled to a Braun Thermoboy circulating temperature
bath which will maintain a constant temperature to
_+0.2°C. For temperatures below room temperature a cold
slush bath was added to the circulating system. The bath
consisted of 1/4" x 10' copper tubing coil suspended in a
dewar containing any number of solvent/CO^ or solvent/N^
2 7
slushes depending on the temperature desired. Methanol
was used as the circulating liquid at low temperatures to
prevent freezing and the sample compartment was continuously
purged with to prevent moisture from condensing on the
sample cell.
Synthesis
Di-cL-chlorotetrakis(ethylene)dirhodium(I),
[Rh(C)^C1 ] 7, was prepared according to a method
2 8
reported by Cramer. A solution of 0.6 g (2.28 mmoles)
RhCl^* 3H20 dissolved in 1 ml of H^O and 7.0 ml
methanol was added to a 125 ml Parr pressure bottle
containing a magnetic stir bar. The mixture was then purged
5 times with ethylene and finally pressurized to 20 psi.
After 15 hours of stirring the solution had changed color
and an orange-yellow precipitate had formed. The solid was

14
filtered and washed with anhydrous methanol in a filled
glove bag and dried for 2 hours over P2O,-. (Caution,
vacuum drying will result in the loss of ethylene from the
complex.) The complex can be stored indefinitely under
at 0°C.
Di-a-chlorotetrakis(tri-p-tolylphosphine)dirhodium(I),
[Rh(P(p-tolyl)^)^C1]2 was prepared by combined methods
8 1
reported by Tolman et al. and Wilkinson et al. . In an
inert atmosphere box 0.266 g [ Rh( C2H4 ) ?C1 ]-, , 0.85g of
freshly recrystallized P(p-tolyl)^ and 17 ml toluene were
placed in a 50 ml round bottom flask equipped with a Vigreux
column. The resulting solution was refluxed with stirring
for 5 hours. While still warm, 35 ml of hexanes were added
and the solution was allowed to cool. The orange
precipitate that formed was filtered, washed with hexanes
and dried for 12 hours under vacuum. This complex is found
to decompose slowly with time and can be purified by
repeated recrystallization in toluene followed by addition
of hexanes. Analysis: C, 67.6; H, 5.7; Cl, 5.0.
Theoretical: C, 67.5; H, 5.7; Cl, 4.8.
Thermodynamic Measurements
Spectrophotometric titration was used to determine the
equilibrium constant of the following reaction:
(P(p-tolyl)3)2RhClB + H2 ~~ ' ( P ( p-t oly 1 )3 ) 2 RhCl B (H )2 (4)

15
Due to extreme 0? sensitivity of the above reaction a
special hydrogen gas flow system was used to vary the
hydrogen partial pressure. A series of preset H-,/N^ gas
mixtures were bubbled through a 0.1 cm UV-vis cell
containing a toluene solution of (P(p-toly1)^^RhClB.
Absorbance changes of the hydrogenated complex in the
visible range (350-650nm) were recorded after equilibrium
was reached with each hydrogen partial pressure.
Equilibrium constants were determined with the
2 9
Gasuptake program developed by Beugelsdijk in which the
best K-'*' and (Eo-E) were simultaneously determined. By
use of the best fit (Eo-E) calculated for each temperature
equilibrium constants were generated for each absorbance
change. These K's were then used in a van't Hoff analysis
to determine AH. In determination of 90% confidence
intervals for AH, a degree of freedom was subtracted for
each temperature used to account for holding the best fit
(Eo-E) constant.
Hydrogen Gas Flow System
A specially designed gas flow system was assembled as
shown in Figure 2-2. Hydrogen and nitrogen gas was first
passed through L.C. Company 0^ traps removing 0^ up to
0.1 ppm. The gases then enter a Matheson (Model 7352)
rotometer fitted with no. 610 tubes where the gases are
accurately mixed to the desired N?/H, ratios. The
no. 610 tubes are the most sensitive flow meters available

Figure 2-2. Gas flow system.

3817-ii
Brass Valves

18
from Matheson and are essential for accurate determination
of N^/H^ ratios.
The mixed gas leaving the rotometer enters a brass
manifold made up of Swaglok hardware including five gas
valves. From here the gas is directed to a specially
designed bubbler containing a toluene solution of the
rhodium chloride dimer. The bubbler saturates the gas with
toluene so that when it is bubbled through the toluene
solution in the UV-vis cell, there is no appreciable
evaporation. The function of the oxygen sensitive rhodium
chloride dimer in the bubbler was to act as a final 07
trap.
The gas now saturated with toluene was bubbled through
the bottom of a highly modified 0.1 cm pathlength barrel
UV-vis cell (Figures 2-3, 2-4) situated in the thermostated
source compartment of a Cary 14 spectrophotometer. The
special cell contained a toluene solution of the solution
generated monomeric rhodium base adduct. Gas exiting the
cell was bubbled through a mineral oil bubbler which
maintained a constant internal pressure in the system. A
mercury monometer present in the system was used to
determine the internal pressure.
Solutions of the various monomeric base adducts were
generated by adding enough of each base to a rhodium dimer
solution to cause greater than 95% cleavage of the dimer.
The amount of each base added was based on equilibrium
30 2 3
constants reported by Farris and Hoselton for the

Figure 2-3. UV-cell.
A. lmm pathlength barrel cell
B. #7 O-ring joint
C. Teflon needle valves

20
Side
Fron t

Figure 2-4. UV-vis cell holder.
A. Thermostated cell holder
B. UV-vis cell
C. Aluminum cell holder
D. Rubber liner

22

23
bridge cleavage reaction. The general operating procedure
of the hydrogen gas flow system is described below in an
example experiment (refer to Figure 2-2).
The UV-vis cell and the toluene bubbler were removed
from the flow system and placed in an inert atmosphere box.
The cell was filled with a toluene stock solution that was
2.02 x 10_^M in [Rh(P(p-tolyl)^Cl]2 and 8.111 x 10 2M
in P(p-tolyl)j. The toluene bubbler was loaded with
toluene that contained a spatula or two of
[Rh(P(p-tolyl)?C1]^. The teflon valves were closed
on both the cell and the bubbler. The cell and bubbler were
then removed from the inert atmosphere box and placed back
into the flow system.
Having all the valves closed except for valves #3, 6
and 9, the system was evacuated by opening valve #10 which
was connected to a vacuum pump. After closing valve #10,
the system was then purged with by opening valve #8.
The evacuation-purge cycle was repeated a minimum of five
times. Following the final purge with , valves #8 and
#6 were closed and valves #4, 5 and 11 were opened.
Valve #8 is opened fully and the rate of N2 bubbling
was now controlled by the rotometer valve. Valve #9, which
is the major bypass valve, is slowly closed until a
satisfactory bubble rate is achieved in the toluene
bubbler. Too high a rate may cause toluene to foam over
into the built in trap.

24
Valves on the cell, #1 and #2, were then opened fully.
Valve #3, a minor bypass valve, was slowly closed until the
desired cell bubble rate was achieved, about 1 bubble per
second. Too rapid a bubble rate may cause evaporation.
After the rhodium monomer solution had come to equilibrium
with the N? in the system, the valves on the cell were
closed and the visible spectrum was recorded.
Valve #3 was opened fully and the rotometer valves were
adjusted to give the first desired hydrogen partial
pressure. The bubbling through the toluene bubbler was
adjusted again by valve #9 and the system was allowed to
purge for 30 minutes. Following purging, the cell valves
were opened and bubbling through the cell solution was
adjusted using valve #3. Once the cell solution had come to
equilibrium, indicated by no further change in the
absorbance spectrum, the cell valves were closed and the
visible spectrum was recorded. This same procedure was
followed for each additional hydrogen-nitrogen gas mixture.
The rotometer was calibrated prior to the experiment
using a soap bubble flow meter connected to valve H7.
Results and Discussions
Fairly extensive thermodynamic and structural studies
have previously been done by Farris'^ and Hoselton25 on
the bridge cleavage reaction (Equation 2) of the chloro

25
bridged dimer [RhCl(P(p-tolyl)^)¿]2 with various
sulfur, nitrogen and phosphorous donor bases. Equilibrium
constants and heats of reaction obtained for the reaction
are shown in Table 2-1.
Based on these results monomer solutions used for the
reaction with hydrogen (Equation 1) were made by adding a
sufficient quantity of base to a rhodium dimer solution to
cleave the dimer by greater than 95%. The ratios of base to
dimer concentration suggested by Farris were as follows:
P(p-tolyl)^, 40:1; THTP, 60:1; pyridine, 40:1. The
resulting monomer solutions were then loaded into the cell
of the specially designed flow system.
Great care was taken to exclude 02 while preparing
the monomer solutions because of their extreme oxygen
sensitivity. Fresh monomer solutions were made before each
experiment in an inert atmosphere box. The rhodium dimer
which was also oxygen sensitive had to be recrystallized
periodically to maintain its purity.
Previously, Farris50 had attempted to determine heats
for the reaction of the various base monomers with molecular
hydrogen using a variable temperature spectrophotometric
titration method utilizing a static gas system. This proved
unsuccessful mainly due to problems with oxygen
contamination.
An alternative to a static type system is a gas flow
type system which was developed for this study (Figure 2-2)
and described in detail in the experimental section. The

26
Table 2-1. Thermodynamic Results for the Interaction of
[RhCl(P(p-tolyl33)2with Various Bases at
24 + 2°C .
Base
a
ah
a
K
b
K (spec )
P(p-tolyl)3
c d
-4.7 + 0.3
e
Large
-
Pyridine
- 4.9 + 0.2
Large
1 8 3 j+ 2 2
THTP
-1.9+0.2
(1.0+0.4)xl02
-
N-methylimidazole
-6.6+0.2
(2.4+2.0)xl04
-
a Determined by Calorimetry.23 b Determined
spectrophotometrica1ly.^0 c Units of Kcal/mole of monomer
formed, d Reported errors are standard deviations.
e Keq. is unknown but assumed to be very large for purpose
of calculating AHav.

27
main advantage of this system is that a positive pressure of
and is maintained throughout an experiment which
reduces the chance of 0^ leaking into the system from the
outside atmosphere. One disadvantage of a flow system is
that care must be taken to prevent solvent evaporation due
to continuously bubbling the various gas mixtures
through the cell solution. This potential problem was
solved first by maintaining a slow continuous bubble rate
through the cell solution and second, by placing a toluene
bubbler in the gas line before the cell. This aided by
prior saturation of the gas with toluene
minimizing any solvent evaporation due to bubbling gas
through the cell.
In order to test the flow system a toluene solution of
air stable tetraphenylporphyrin solution was placed in the
cell of the flow system. After 2 hours of continuously
bubbling N2 through the solution, there was no significant
change in its UV-visible spectrum indicating that the
toluene bubbler was effectively preventing solvent
evaporation.
The changes that occurred in the electronic spectra
upon bubbling various partial pressures of hydrogen through
solutions of (P(p-toly1)^)2RhClB are illustrated in
Figures 2-5 and 2-6 for the bases P(p-tolyl)^ and THTP
respectively. In both cases the shoulder (centered at
430nm for P(p-tolyl)^ and 420nm for THTP) on the side of

Figure 2-5. UV spectrum of a toluene solution of 1.86x10'%
[RhCl(P(p-tolyl)3)2]2. and 7.47x10'%
P(p-tolyl)3 at 35.0°C in equilibrium with
various pressures of H2 . (1: Ph2 = 0-00 atm,
2: Pjq2 = * 02 3 atm, 3: P^2 = *045 atm,
4; Ph2 = .075 atm, 5: P^2 = -145 atm,

29
\ .0
o

Figure 2-6. UV spectrum of a toluene solution of 2.98xlO“^M
[RhCl(P(p-tolyl)3]2, and 5.79xlO"2M THTP at
10.0°C in equilibrium with various pressures
of H2. (1: Ph2 = 0-00 atm, 2: P¡_j2 = -015 atm
3: ?H2 = «102 atm, 4: P2 = .217 atm
5: Pjq2 = *965 atm.)

Absorbance
31
Wavelength, nm

32
a large charge transfer peak decreased in intensity as the
concentration of increased.
An isobestic point was observed in the P(p-tolyl)j
system at about 350nm probably indicating that only two
chromophors were present in solution and that the rhodium
monomer was being cleanly converted into the six coordinate
cis-rhodium dihydride complex. This provided further
evidence supporting what had previously been shown by NMR
studies of the reaction. (Caution must be taken not to rely
solely on the appearance of an isobestic point. An
additional experimental method should be used to determine
the actual reaction taking place.)
The spectral data obtained were analyzed using the
Rose-Drago^1 equation (Equation 5)
3 2
which was modified for the hydrogen uptake experiment.
In this equation is the hydrogen partial pressure
bubbled through the solution, b is the pathlength of the
cell, A is the initial concentration of the acid (Rh
o
monomer), A is the absorbance of the cis dihydride complex,
A° is the absorbance of the acid solution (with no H7
present), (Eo-E) is the difference in the molar absorptivity
between the hydrogenated and monohydrogenated complex and
K 1 is the inverse of the equilibrium constant for the
reaction.

33
The spectral data and the best determined K and (Eo-E)
values at various temperatures are listed in Table 2-2 for
the bases P(p-tolyl)j and THTP. An equilibrium constant
8 -1
previously reported by Tolman et al. of 40 +_ 3 atm at
25°C corresponds well with the results of this study where
at 30.1°C a value of 29.9 _+ .26 atm ^ was obtained.
Attempts to study the pyridine adduct produced
inconsistent results. This system, unlike the previously
described base adduct systems, was not as well behaved and
presented a number of complications. The first complication
encountered was the extreme 0^ sensitivity of the pyridine
system. Additional precautions to exclude 0^ had to be
taken during the generation of the monomer solutions and
when flushing the flow system.
Initial spectral results established that the
equilibrium constant for the pyridine system was at least an
order of magnitude greater than was observed for the
P(p-tolyl)^ and THTP adducts. This was a problem because
the lowest possible partial pressure that could be
accurately delivered by the rotometer was converting most of
the pyridine monomer into the hydrogenated form.
To overcome this problem, another Matheson rotometer
was added to the flow system. The rotometers were connected
in series as illustrated in Figure 2-2. Rotometer 1 diluted
the with N^. The mixture then entered the second
rotometer reducing the concentration with once
again. The double dilution feature of the system allowed

34
Table 2-2. Thermodynamic Data for the Reaction of
RhClB(P(p-tolyl)3)2 + H2ARhClB(P(p-tolyl)3)2H2.
B
Temp (°C)
a
K
P(p-tolyl)3
9.0
113.7
30.1
29.9
35.0
24.4
44.0
12.2
53.8
7.27
b
c
AH = 11.0 +
. 5 Kcal/mole
THTP
10.0
77.4
15.0
47.6
20.6
33.9
30.0
21 . 5
40.0
13. 2
50.0
5.91
b
c
AH = 11.6 + 1
.0 Kcal/mole
a Best fit K. b Determined by van't Hoff analysis,
based on generating an equilibrium constant for each
absorbance change after the best Eo-Ewas determined and
held constant. c 90% confidence interval.

35
for the accurate delivery of the very low H^N., ratio
gas needed.
A problem encountered which was mainly responsible for
the inconsistent results obtained was the observation of a
slow secondary reaction occurring during the course of the
hydrogen uptake experiment. As seen in the other base
systems, reduction in the shoulder absorbance was observed
on exposing the pyridine monomer solution to various H?
partial pressures. Once the solution had come to
equilibrium with a hydrogen partial pressure, the shoulder
absorbance increased slowly with time instead of remaining
constant. This phenomenon is attributed to a slow secondary
reaction taking place, possibly due to the presence of a
large excess of pyridine in solution with the newly formed
rhodium dihydride complex. (As in the pyridine
experiments, similar problems were encountered with the
1-methy1imidazole adduct experiments.)
The two systems that could be investigated
(P(p-tolyl)^ and THTP) fortunately provided a substantial
variation in the strength of binding to the Rh(I) center.
Enthalpies of hydrogen binding were determined by use of the
van't Hoff equation where a plot of -RlnK vs. 1/T yields a
straight line with a slope of AH and an intercept of AS.
-R Ln K = AH - AS
T
(6)

36
Due to the large error limits involved with
calculating AH from a plot of only five or six points
corresponding to K at each temperature, a method suggested
by Breese^ was employed to utilize all of the data
obtained in the equilibrium constant experiments. His
method involves calculating the best K and (E -E) at each
temperature. The best (E -E) at a specific temperature is
then substituted into the Rose-Drago equation and an
equilibrium constant is calculated for each absorbance
change. Thus a number of equilibrium constants were
determined at each temperature (Table 2-3) instead of only
one. The end result was a AH with a much smaller error
limit. Care must be taken in determining standard
deviations to reduce the degrees of freedom by one for every
temperature to account for fixing the value of ( Eq-E) .
The van't Hoff plots obtained are shown in Figures 2-7 and
2-8 respectively for the P(p-tolyl)^ and THTP systems.
The enthalpies obtained are shown in Table 2-2. These
enthalpies can be combined with the heat of dissociation of
H^ to produce the average metal-hydrogen bond dissociation
energies (Table 2-4).
RhClB(P(p-tolyl)3)2(H)2 > RhClB(P(p-toly1)3)2 + H2 (7)
H2 >2H- (104.2 kca1 mole-1) (8)
RhClB(P(p-tolyl)3)2(H)2 >RhClB(P(p-toly1)3)2 + 2H- (9)

37
Table 2-3. Thermodynamic Data on
RhCl(P(p-tolyl )3)2 B + H2 <—» RhCl(P(p-toly1)3)2BH2.
B
(Rh)(M) Pu (atm) Abs K
2
P(p-tolyl)3
Temp.
Temp.
Temp.
Temp.
Temp.
9.0°C
4.05
X
10 "3
. 0246
.356
108.5
(Eo-E)a = 1209
4.05
X
10"3
. 0490
.421
125.0
Ka = 113.7
4.05
X
10"3
.0813
.444
119.7
CSD =3.8
4.05
X
10“3
.156
.465
120.6
MSD/CSDb =1.4
4.05
X
10“3
.392
.477
96. 2
4.05
X
10“3
. 981
.483
74. 1
30.1°C
4.05
X
10 ‘3
.0237
.158
29.3
(Eo-E) = 951.3
4.05
X
10-3
.0474
.227
30. 2
K = 29.9
4.05
X
10'3
. 0786
.270
29.8
CSD = .26
4.05
X
10‘3
.151
.317
30. 7
MSD/CSD =1.5
4.05
X
10"3
.379
.354
29.9
4.05
X
10'3
.948
.371
27.4
35.0°C
3.72
X
10 "3
. 0227
.135
21 . 8
(Eo-E) = 1095
3.72
X
10"3
.0454
.221
26.1
K = 24.4
3.72
X
10‘3
. 0752
.267
25.3
CSD = .85
3.72
X
10 "3
.145
.318
24. 6
MSD/CSD =1.5
3.72
X
10"3
.363
.364
23.1
44.0°C
4.05
X
10'3
. 0224
.087
12.1
(Eo-E) = 1007
4.05
X
10'3
.0449
.141
11 . 8
K = 12.2
4.05
X
10"3
.0741
.194
12.2
CSD = .19
4.05
X
10‘3
.143
.263
12.7
MSD/CSD =1.7
4.05
X
10“3
.359
.334
12.6
4.05
X
10’3
.898
.371
11.2
53.8°C
4.05
X
10 ’3
. 0423
.090
6.3 7
(Eo-E) = 1047
4.05
X
10'3
.0701
.139
6.96
K = 7.27
4.05
X
10 "3
.135
.217
7.78
CSD = 3.7
4.05
X
10'3
.338
.310
8.04
MSD/CSD =1.9
4.05
X
10'3
.844
.358
6.4 1

38
Table 2-3. - Continued
B
(Rh)(M)
(atm)
Abs
c
K
THTP
Temp. = 10.0°C
5.66
X
10 “3
.0147
.256
78.0
(Eo-E ) = 847
5.66
X
10
.102
.423
73.6
K = 77.4
5 66
X
10 "3
.217
.453
79.0
CSD = .99
5.66
X
10“3
.371
.464
81 . 2
MSD/CSD =1.2
5.66
X
10"3
.966
.474
90. 9
Temp.
= 15.0°C
6 54
X
10"3
.0147
.178
47. 1
(Eo-E) = 66 7
6.54
X
10 "3
.102
.365
50.0
K = 47.6
6.54
X
10 "3
.217
.397
46.2
CSD = .94
MSD/CSD = 1.4
6 54
X
10"3
.371
.412
45.3
Temp.
= 20.6°C
4 75
X
10 _3
.0144
.078
33. 6
(Eo-E) = 505
4.75
X
10'3
. 0456
.144
33.0
K = 33.9
4.75
X
10"3
.0993
.188
36. 4
CSD = .68
4.75
X
10‘3
.212
.211
34. 4
MSD/CSD =1.5
4.75
X
10 “3
.363
.222
34. 3
4.75
X
10‘3
.946
.231
27 6
Temp.
= 30.0°C
5 14
X
10"3
.0142
.058
18.5
(Eo-E) = 541
5.14
X
10'3
.0986
.195
23.8
K = 21.5
5.14
X
10‘3
.210
.229
22.2
CSD =1.1
5.14
X
10-3
.359
.245
20.6
MSD/CSD =1.8
5.14
X
10“3
.932
.262
17.5
Temp . = 40.0°C
5.04
X
lO’3
.0136
.030
12.1
(Eo-E) = 4 4 2
5.04
X
10"3
.0946
.113
12.1
K = 13.2
5.04
X
10’3
.202
.159
15.0
CSD = .31
5.04
X
10“3
.344
.180
16.53
MSD/CSD =2.2
5.04
X
10"3
. 898
.189
9. 3
Temp .
= 50.0°C
5.98
X
10 ’3
.0131
.018
2.69
(Eo-E) = 883
5.98
X
10 “3
.0912
.190
6. 1 8
K = 5.91
5.98
X
10"3
.194
.283
5.95
CSD = .31
5.98
X
10'3
.331
.350
5.93
MSD/CSD =2.2
5.98
X
10“3
.864
.440
5.80
Best
fit K and (Eo-E).
b CSD
i s
conditiona1
s tandard
deviation and MSD is marginal standard deviation for best
fit K. c Equilibrium constant for each absorbance change
after best fit (Eo-E) was determined and held constant.

Figure 2-7. Van't Hoff plot for the P(p-tolyl)3 system.

40
o

Figure 2-8 .
Van't Hoff plot for the THTP system.

Ln K
42
o

43
Table 2-4. Average M-H Bond Energies.
Compound AH (av.M-H) Kcal/mole
Rh(P(p-tolyl)3)3Cl(H)2
57.6 + .3
Rh(P(p-tolyl)3)2(THTP)Cl(H)2
57.9+ .5
Ir(CO)XL2H2 3
r
57-61
b
Co-H
39 + 6
a L. Vaska and Werneke.-^ b j. Beauchamp and
Armentrout . ^5

44
Comparing the values obtained for the two base
systems, it is immediately apparent that within
experimental error the average metal-hydrogen dissociation
energies are identical. Thus the rhodium-hydrogen bond
strength was found to be insensitive to varying one ligand
around the rhodium center.
Based on the observation that two vastly different
bases (P(p-tolyl)^ and THTP) had little or no effect on
the Rh-H bond strength, it is probably safe to assume that
other donor bases, such as pyridine, would also have little
effect on the Rh-H bond dissociation energy. Thus the
adverse effects the addition of pyridine (mentioned in the
introduction) has on hydrogenation by Wilkinson's catalyst
is probably due to factors other than those affecting the
catalyst's metal hydrogen bond strength.
A variable temperature ^HNMR study reported by
2 2
Hoselton et al. showed that that following kinetic
process was taking place in the presence of excess pyridine
H
K
H
(10)
B
Cl
B = Py
The pyridine which is trans to a hydride was shown to
exchange with free pyridine in solution. A proposed
intermediate in the reaction was a trigonal bipyramid

45
"Rh(P(p-toly1),)7C1(H)species. The incoming
pyridine could attack a position trans to either hydride
which would account for the observed averaging of the two
inequivalent hydride resonances with increasing temperature.
A similar kinetic process was reported for an analogous
Wilkinson's catalyst system, Rh( P ( C^Hj-) ^ )jCl (H)^ , by
O
Tolman et al. . The first order rate constants observed for
exchange of pyridine and P(C^H^)^ for the similar
intermediate were 50 sec ^ and 1000 sec ^ respectively at
25°C. This ligand exchange process serves a very
important role in the proposed mechanism of Wilkinson's
catalyst in that it provides an important open coordination
site for the binding of an olefin. The fact that the rate
of ligand exchange involving pyridine is an order of
magnitude smaller than that observed for PCC^H^), may
account for added pyridine having adverse effects on
catalytic activity due to efficient competition for the
olefin binding site by pyridine.
The metal hydrogen bond energies determined can be
compared to others reported in the literature (Table 2-4).
In a study^’^ 0f the influence of ligand variation in
the system IrCCCOXL^ (where L is a series of phosphines
and X is Cl , Br , and I ), enthalpies of
hydrogenation of 2.7 to 18.1 kcal mole ^ were measured
corresponding to average metal hydrogen bond energy
variations of 55 to 61 kcal mole ^. The gas phase neutral

46
Co-H bond dissociation energy, determined by ion beam
techniques,^ was reported as 39+_6 kcal mole ^.
Conclusion
The main purpose of this study was to investigate the
process of hydrogen activation by transition metals and to
understand what effect ligand environment has on the metal
hydrogen bond dissociation energy.
The enthalpy of hydrogen activation by
Rh(P(p-tolyl)2C1B was obtained for B = P(p-tolyl)^
and THTP. Attempts to determine enthalpies for pyridine and
N-methylimidazole systems were unsuccessful. The enthalpies
that were obtained were used to determine average metal
hydrogen bond dissociation energies. This provided a good
estimate of the hydrogen bond energies associated with a
good hydrogenation catalyst (Wilkinson's catalyst) and with
one of its derivatives. It also greatly increased the
amount of available data presently in the literature.
The two bases THTP and P(p-tolyl)^ fortunately were
substantially different so that the effect of ligand
variation could be observed. The equilibrium constants
obtained for Equation 1 parallel the basicities of the two
bases toward the rhodium (I) center. However, the
enthalpies obtained for the two systems were remarkably
3 7
independent of the donor strength. Thus the average

47
meta1-hydrogen bond energy was found to be insensitive to
differences in the two ligands. Assuming this result could
be extended to the pyridine system, the adverse effects of
adding pyridine to the catalytic system are probably not due
to pyridine's effect on the catalyst's metal hydrogen bond
strength but more likely due to pyridine blocking important
coordination sites on the catalyst.
A final outcome of this study was that a convenient
method was developed for the determination of enthalpies of
hydrogen activation.

III. IMMOBILIZED HOMOGENEOUS CARBON MONOXIDE
REDUCTION CATALYSTS
Introduction
Immobilization of homogeneous transition metal
catalysts on various organic or inorganic supports, often
termed "hybrid"^ or "HETMETCO"^ (heterogenized
transition metal complex) catalysts, is presently a very
exciting and active field of catalysis research. The over¬
riding goal in this area of research is to combine the
advantages of heterogeneous and homogeneous catalysts, while
minimizing their inherent deficiencies. A fair number of
articles have been published reviewing the growing volume of
reported studies involving synthesis, characterization and
catalytic properties of supported homogeneous catalysts'^ ^
A list showing the major advantages of heterogeneous
vs. homogeneous catalysts is given in Table 3-1.
Heterogeneous catalysts, viewed by many as being first
generation catalysts, have been widely used in industry for
many years. One of the major advantages of these catalysts
is their ease of separation from reaction products. Other
advantages are that heterogeneous systems are generally more
thermally stable and less corrosive than homogeneous
systems. A major drawback that has hindered the development
of heterogeneous catalysts has been the limited number of
48

49
physical techniques available to characterize these
systems. Although numerous studies over the years have
revealed, little information about the actual active
catalyst species, recent advancements in surface techniques
such as SEM, ESCA, XPS, Auger etc. have provided a better
understanding of the nature of these catalysts.
Table 3-1. Advantages of a Homogeneous Versus Heterogeneous
Catalysts.
Homogeneous
vs.
Heterogeneous
1.
more active
1.
separation of catalyst
from product
2.
reproducible
2.
minimizes reactor
corrosion
3.
milder operating
conditions
3.
more thermally stable
4.
characterization
5.
more selective
Homogeneous catalysts, termed second generation
catalysts, are in many ways superior to heterogeneous
systems. These catalysts are generally more active, more
selective, and because these catalysts are derived from
discrete soluble transition metal complexes they lend
themselves to study by a large number of physical methods.
They have the advantage that their properties can be widely
varied by changing the ligand environment around the metal

50
center and because the composition of the catalyst or
catalyst precursor is known these systems are very
reproducible.
Industrially, homogeneous catalyst systems are much
harder to handle then heterogeneous catalyst systems. One
major problem involves the separation of the often precious
metal catalyst from the reaction products. Usually, unless
the reaction products can be easily distilled from the
reaction mixture, such as in the Monsanto^ process for
the carbonylation of methanol to acetic acid, the
catalyst-product separation can be a very costly process.
Other disadvantages of homogeneous systems are that they are
generally more corrosive than heterogeneous systems, and the
reaction medium is limited to the solvents in which the
catalyst is soluble.
Immobilization of homogeneous catalysts may not only
combine the advantages of homogeneous and heterogeneous
catalysts but has the potential for some new desirable
features. One feature is site isolation of catalytic
species. This would prevent catalyst site interactions
which are often a mechanism for catalyst deactivation.
There is also the potential for site interaction between
similar or different catalytic sites placed in close
proximity to one another. This could possibly mimic some of
the chemistry demonstrated by enzyme systems.
In this study attention will be focused on the use of
immobilized homogeneous catalysts in the area of carbon

51
monoxide reduction catalysts. Known homogeneous ruthenium
and iridium CO reduction catalysts have been ionically or
covalently attached to inorganic supports. The development
of these catalysts was geared toward discovering catalysts
capable of selectively producing chemicals from mixtures of
CO and gases, referred to as "syngas," under very mild
reaction conditions. The supports chosen were silica gel
and alumina functionalized by various órganos i1anes.
In the course of this study a novel catalytic system
for the selective conversion of syngas and HC1 to
chloromethane was discovered (Equation 1).
h2 + CO + HC1 h2o + ch3ci (1)
This reaction occurs under extremely mild conditions, 25°C
and 1 atmosphere pressure, and has the potential to be an
industrially significant process.
Processes involving the conversion of syngas, such as
the Fischer-Tropsch synthesis^ described in Equation 2,
have been known and extensively studied and reviewed since
the early 1900's.^ ^0 in the last decade concerns over
dwindling petroleum supplies have sparked a renewed interest
CO + H2 catalysts ^ Hydrocarbon Products (2)
(Alkanes, Alkenes, Oxygenates)

52
in the utilization of syngas as a viable source of chemicals
and motor fuels. The Fischer-Tropsch process, which
operates at elevated temperatures and pressures, utilizes a
heterogeneous catalyst usually consisting of one of the
three metals Fe, Co and Ru. The major disadvantage of the
Fischer-Tropsch synthesis which has plagued its development
since its discovery is its inherent lack of selectivity.
51 5 2
Early studies ’ demonstrated that the product
distribution produced by traditional Fischer-Tropsch
catalysts obeys the simple polymerization model below
(Schutz-Flory distribution), Equations 5 and 4. This model
assumes chain growth occurs by incorporation of single
carbon fragments and that the probability of chain growth is
Wn
= n
(1 - o<
)2 o< n-1
(3)
=
r£.
(4)
rP +
rt
independent of
chain
length.
The term Wn
represents the
weight fraction
of a
certain
carbon number
n,
is defined
as the probability of chain growth and is equal to the rate
of polymerization divided by the sum of the rate of
polymerization and the rate of termination, and (1 - <*.)
represents the probability of chain termination.
In order to improve selectivity one needs to deviate
from this type of Schultz Flory kinetics. Recently, there
have been a number of reports'^ of product distributions
deviating significantly from this polymerization model.
Product distributions have been altered by using new metal

53
5 4 5 5
loading techniques, selective catalyst poisoning
(i.e. partial sulfiding) and the use of shape selective
supports such as zeolites.^ ^ Although these reports
look promising, further work needs to be done to establish
whether these effects are experimental artifacts or are due
to actual mechanistic effects.
Due to their potential for greater product selectivity,
homogeneous carbon monoxide reduction catalysts have been a
subject of active research in the last decade. A number of
systems involving primarily cobalt^’^0 rhodium^ > ^ 2 or
ruthenium^’^ have been developed for the production of
mixtures of oxygenated products (i.e. methanol,
methylformate, ethylene glycol) but most operate under
extreme conditions, with pressures usually exceeding 1000
atmospheres.
More recently several homogeneous systems have been
developed which operate under moderate conditions (below
1000 atmospheres). Knifton^ at Texaco reported an active
catalyst for the direct synthesis of ethylene glycol from
syngas at 430 atmospheres and 140-250°C. The catalyst
consisted of a number of ruthenium precursors dissolved in a
highly polar molten quaternary phosphonium salt. The active
catalyst species based on IR and NMR studies was
believed to be the anion [HRu^(CO)-^ ] .
Two ruthenium based systems were reported by
£ cn
Dombek0 ’ at Union Carbide. The first involved the
monomer Rh(C0)<., evidenced by high pressure IR and

54
believed to be the active catalytic species for the
conversion of syngas to methanol at 230°C and 340
atmospheres pressure. The addition of carboxylic acids was
found to promote the formation of glycol esters.
The second system involved a substantially more active
ruthenium catalyst promoted by ionic iodide promoters and
polar solvents. At 230°C and 850 atmospheres H., and CO,
the primary product was free ethylene glycol. The catalyst
precursor, Ru^CCO)^ was thought to be converted to the
two anions [Ru(C0)^I^] and [HRu^(CO)^] by the
reaction below (Equation 5) in a 2:1 ratio which was found
to be the optimum ratio for maximum ethylene glycol
production. The absence of either one of the anions results
in an inactive system.
Ru3(C0)12 + 31- + H2 > 2 [ HRu3( CO ) ]_ ]_ ] " + [Ru(C0)3I3]“ + 3C0
(5)
In 1977 Muetterties and coworkers^8’^^ reported a
novel homogeneous system which converted syngas to light
saturated hydrocarbons under very mild reaction conditions,
180°C and 1-2 atmospheres pressure (Equation 6). The
catalyst consisted of the cluster Ir^CCO)^ an a NaCl-AlCl,
Ir4(C0)12
CO + 3H2 >CX to C4 alkanes, (CH3C1) (6)
A1C13-NaCl melt
180°C, 1-2 atm
melt solvent and is the first reported homogeneous system
capable of producing non-oxygenated products from syngas.

55
This report was most significant in that it demon¬
strated the importance of Lewis acid interactions with metal
bound CO, such as demonstrated below, allowing the CO to be
7 0
reduced under mild conditions. Studies by Coliman et al.
M C= 0 • • • A1 Cl5
further substantiated the above finding but also showed that
methylchloride was a reaction product, indicating AlCl^
was being consumed during the reaction.
7 1
A similar system reported by Muetterties and Choi
showed that Os^CCO)^ a BBr^ melt was also an active
catalyst for the production of light alkanes under similar
conditions and in this case methylbromide vías detected as a
reaction product.
Methylchloride is an important commodity chemical and
its uses and corresponding consumptions in 1977 are listed
in Table 3-2.
Table 3-2. Consumption of Methyl Chloride - 1977.
Uses
Thousands of Metric Tonsa
Methylchlorosilanes
175
Tetramethyl Lead
51
Butyl Rubbers
23
Other
28
Total
277
a Data obtained from "Chemical Economics Handbook"^

56
7 3
The two principal commercial processes for
producing chloromethane are the chlorination of methane and
the methanol-hydrogen chloride process shown below
(Equations 7 and 8). The chlorination of methane process
> 400°C
Cl2 + CH4 >CH3C1 + HC1 (7)
> 280°C
CH30H + HC1 >CH3C1 (8)
can be accomplished with or without a catalyst. Typical
catalysts for the process are KC1 , CuCl, and CuCl^ melts.
Although the primary product of the process is chloromethane
other multichlorinated methanes are produced as well.
Presently, the preferred process is the methanol-HCl route,
which is very selective for chloromethane, up to 97.8%.
Typical catalysts for this process are gamma alumina or
phosphoric acid on activated carbon.
An alternative synthesis reported in 1977 by
7 4
Vannice at Exxon demonstrated that syngas plus a
chloride source, such as Cl¿ or HC1, could be used to
produce chlorinated hydrocarbons at 200 to 1000°C and 0.1
to 500 atmospheres pressure. The system consisted of a well
dispersed supported catalyst containing Pt/Re, Pt/Ir, Pt ,
Ir, or Re on an acidic support such as alumina. The
predominant product was methyl chloride but other products

57
such as multichi orinated methanes, ethene, propane and butyl
halides were also produced.
Over the years a large number of supports, both organic
and inorganic, have been utilized to heterogenize transition
metal catalysts. A fairly complete list^ is shown in
Table 3 - 3.
Table 3-3. Materials Used to Support Metal Complexes.
Inorganic3
Organic3
silica
polystyrene
zeolites
polyamines
glass
silicates
clay
polyvinyls
metal oxide
(i.e. AI2O3,
polyallyls
T i O2 , Mg 0)
polybutadiene
polyamino acids
urethanes
acrylic polymers
cellulose
cross-linked dextrans
agarose
3 List obtained from Hartley and Vezey.40
In the work presented here both functionalized silica
gel and alumina supports were used to ionically attach known

58
homogeneous CO hydrogenation catalysts. The choice of these
supports over other available supports was based on their
thermal stability, their intrinsic acidic nature, and the
large variety of silanes (containing functional groups) that
can be bond to the surface ferr metal attachment.
The surface of these supports consists of hydroxyl
groups which can react with silanes of the formula
R^Si(CH2)xB (R=C1, OEt, OMe) by way of the simple
7 5
condensation reaction shown in Equation 9.
) (OH|3_y
* ¿-0-S,(CH2)xB + 3 ETON (9)
/
)
)H -i- (OEt)3S,(CH2¡xB
)H
The symbol B represents any number of heteroatom groups
(i.e. -P(Ph)-,, -NH^ , -SH) linked to the surface by a
variable length organic chain. The letter Y represents the
number of Si-O-Si bonds to the surface, which is dependent
7 6
on the concentration of organosilane being used. These
attached organosilanes can be used directly or modified to
support transition metal complexes. The B groups used in
the work presented here were -P(Ph)2 and -N(CH^)3+I .

59
Experimenta 1
Reagents
All solvents and reagents were used as purchased unless
otherwise stated. Triethoxypropy1 aminos i1ane and
2-(diphenylphospho)ethyltriethoxysilane were purchased from
Petrarch Chemical. Iridium trichloride • BH-^O, Ir^CCO)^ and
Rh^(CO)-^^ were purchased from Strem. Triruthenium
dodecacarbonyl, Rul_ and [RhClCCO)^^ were purchased
from Alfa. Sodium chloride was dried prior to use in an
oven at I40°C.
Hydrogen was purchased from Air Products. Both carbon
monoxide grade C.P. 99.5% and hydrogen chloride technical
grade 99.0% gas were purchased from Matheson.
Silica gel was purchased from W.R. Grace and was
Davison grade #62. Its wide pore diameter was 14 mm, pore
3 2
volume was 1.1 cm /g and had a specific area of 340 m .
Alumina used was Acid, Brockman Activity I, mesh 80-200.
ZnO was purchased from Aldrich.
Ins trumenta tion
All air sensitive manipulations were performed in a
Vacuum Atmosphere Co. model HE-43-2 inert atmosphere box.
Elemental analyses were performed by the Microanalytica1
Laboratory, (C,H and N) University of Florida, Gainesville,

60
Florida, and by Galbraith Laboratories Inc. (Ir and P by
ICP) Knoxville, Tennessee.
GC analyses were performed on two different gas
chromatographs. One was a model 3700 FID/TC Varian gas
chromatograph equipped with a 1/16 inch x 1 meter stainless
steel column packed with Chromosorb P supported diethylene
glycol adipate (DEGA)and a 1/16 inch x 10 foot stainless
steel Poropak Q column. The other was a model 940 FID
Varian gas chromatograph equipped with a 1/16 inch x 8 foot
stainless steel Poropak Q column.
Infrared spectra were recorded on a Perkin Elmer 283B
spectrometer and also on a Nicolet 20DX using diffuse
reflectance (spectra performed by Nicolet).
GC mass spectrometry was performed on a AEI MS30 mass
spectrometer using a KOITOS DS55 data station and equipped
with a PYE Unicam 104 GC containing a 1/4 inch x 5 foot
Poropak Q column. Samples were run by Dr. R. King at the
Microanalytical Laboratory, University of Florida,
Gainesville, Florida.
Fixed Bed Flow Reactor
A specially designed gas flow system was assembled as
shown in Figure 3-1. Hydrogen and carbon monoxide first
enter a Matheson (model 7352) rotometer fitted with No. 610
tubes where the gasses were accurately mixed to the desired
H^CO ratio. When needed, HC1 gas was passed through a
Matheson #601 flow meter where it was combined with the

Figure 3-1. Fixed bed flow reactor.

Bubbler
Septum
Ü
^J
Trap
B
S ¿
IS
IT
Septum
mum
t\J
Bubbler C
;H2 gas
:C0 gas
Bubbler D
HCI gas

63
already mixed syngas. The amount of HC1 added was regulated
by teflon needle valve HI. Problems were encountered with
maintaining an even flow of HC1 , and a pressure release
bubbler (D) placed before the flow meter proved helpful.
The gasses then were passed through the catalyst bed which
consisted of a powder catalyst packed on top of a glass frit
and held in place with a plug of glass wool. The gasses
leaving the reactor tube were then passed through a
CO^/acetone cold trap and exited finally through a mineral
oil bubbler. The reactor contained two septa for syringing
gas samples for analysis before and after the reactor. The
flow of gasses through the catalyst was regulated by the
teflon needle valve #2. As this valve was closed, a greater
amount of the feed gas was forced through the reactor tube
as opposed to exiting through the mineral oil bubbler (C).
The reactor was designed so that the reactor could be
assembled in an inert atmosphere box. The bypass arm B was
designed for purging the system.
Surrounding the reactor tube was a Lindberg (model
123-8) thermostated tube furnace used to regulate the
reactor temperature. The entire system was made of glass
or teflon tubing due to the corrosive nature of HC1 gas.
Synthesis
Silica Gel Bound Propylaminosilane (silica gel)-^/NNH2
The functionalized support was prepared by a method
7 7
reported by Leyden et al. In a 125 ml Erlenmeyer flask,

64
10 g of silica gel was combined with 50 ml toluene. After
stirring for 10 minutes, 5 ml of triethoxypropylam i nos i1ane
was added. The mixture was stirred for an additional
30 minutes, filtered and the solid was washed with copious
amounts of toluene. The solid was air dried followed by
heating in an oven at 80°C for 24 hours. Analysis: C,
3.74%; H, 1.08%; N, 1.40%. (Theoretically represents
1.0 mmole silane per gram silica gel.)
Trimethylammonium Iodide Salt of Silica Gel Bound
Propylaminosilane (silica gelN(CH^)^1
The functionalized support was prepared by a method
7 8
reported by Zombek. In an Erlenmeyer flask equipped
with an addition funnel and blanketed with N?, 10 g of
propylaminosilane bound silica gel, 1.13 g 2,6-lutidine and
80 ml DMF were combined. A solution ( 30 ml) made up of
5.67 g Mel in DMF was added dropwise to the mixture while
stirring. Stirring was continued for 15 hours at ambient
temperature. The reaction mixture was filtered and the
solid washed with acetone and benzene followed by vacuum
drying (0.1 mm Hg) for 24 hours. Analysis, C, 4.52%; H,
1.30%; N, 1.22%; I, 8.37%. (Theoretically represents
.68 mmole trimethylpropylainmonium iodide groups per gram.)
Silica Gel Bound Phosphine Silane (silica g e 1) P ( Ph)-,
The synthetic method was patterned after a preparation
7 9
reported by Schrader and Studer. Silica gel (5.0 g)

65
was dried under vacuum at 32 5 °C for 4 hours. In a two
neck 30 ml round bottom flask equipped with a reflux
condenser and a rubber septum in a nitrogen filled glove
bag, the silica gel and 100 ml of 3:1 benzene:p-dioxane
(each distilled from CaH^) were combined. The apparatus
was flushed with N7 for 1/2 hour while vigorously-
stirring. The stirring rate was reduced, 0.45 ml of
2-(diphenylphospho)ethy1triethoxysi 1ane was syringed in and
the mixture was refluxed for 12 hours. After cooling, the
solid was filtered in a glove bag, washed with benzene and
dried under vacuum for 24 hours at 25°C.
Silica Gel Bound Phosphine Silane (High Loading)
The same procedure was used as described above for
(silica gel) P(Ph)7 except the amounts of reagents used
were 2 g silica gel, 100 ml 3:1 benzene:p-dioxane and 0.9 ml
2-(diphenylphospho)ethyltriethoxysilane.
Alumina Bound Phosphine Silane (alumina) P(Ph)7
Alumina (10 g Acid Brockman Activity I mesh 80-200) was
washed with dilute HC1 and dried in an oven at 90°C for
12 hours. In a 500 ml two neck round bottom flask equipped
with a reflux condenser and a rubber septum, the alumina and
200 ml of xylenes were combined. The mixture was degassed
by bubbling N? through the suspension while stirring for
1.5 hours, followed by syringing in 1.5 ml
2-(diphenylphospho)ethyltriethoxysilane and refluxing for

66
12 hours under . After cooling the solid was filtered,
washed with xylenes, toluene, and absolute ethanol followed
by drying at 100°C for 24 hours.
[ NE t4 ] [ RU3H (CO ! ]
A procedure was used similar to the synthesis reported
8 0
by Lewis et al. All manipulations were performed in an
inert atmosphere box, or with Schlenk-ware techniques. In
a flask, 0.3291 g Ru3(CO)12, 0.1035 g NaBH4 and 50 ml
tetrahydrofuran (degassed, distilled over CaH2) were
combined. After stirring for 30 minutes the solution
turned deep red. The mixture was filtered through a frit
and the THF was removed under vacuum. The reddish residue
was then combined with 20 ml of degassed methanol followed
by the addition of 0.132 g tetrae thy1ammoniurn bromide
dissolved in 5 ml methanol. The volume was reduced to
10 ml followed by cooling overnight in a CO^/acetone
bath. The precipitated solid was filtered, washed with
a small amount of -78°C methanol and dried under vacuum
for 24 hours. Analysis: C, 29.38%; H, 3.53%; N,
1.73%. Theoretical: C, 30.75%; H, 2.85%; N, 1.90%.
(Problems were encountered during analysis due to 0^
sensitivity.)

67
[Cs][Ru(CO)3)3]
A procedure was used similar to that reported by
81
Griffith and Cleare. In a 100 ml round bottom flask
equipped with a reflux condenser, 1.1 g anhydrous Rui,.,
8.3 ml hydroiodic acid and 8.3 ml formic acid were
combined. The mixture was refluxed and stirred for 12
hours. After cooling, the mixture was filtered and 0.83 g
CsCl was added to the filtrate. The solvent was removed on
a rotary evaporator, the residue was extracted with absolute
ethanol and the solvent was then removed again. Analysis:
C, 4.2%; I, 54.8%. Theoretical: C, 6.2%; I, 54.5%. The
brownish- yellow residue was recrystallized in absolute
ethanol.
Silica Gel Functionalized [Rul3(CO)3]" and [HRu3(CO)^i ] “
In a 50 ml Erlenmeyer flask 0.1136 g of the ammonium
iodide salt of silica gel bound propy1 aminosilane (8.37% I),
0.0222 g Cs[RuIj(CO)^] and 20 ml of tetrahydrofuran were
combined. The purple mixture was heated while stirring and
remained at reflux temperature for 10 minutes. After
cooling, the light maroon solid was filtered and washed with
THF. The resulting solid was brought into an inert
atmosphere box and combined with an intensely maroon colored
solution consisting of[NEt^][HRuCO)^^ ] dissolved in
5 ml of THF. After the mixture was stirred for 10 minutes,

68
the light maroon colored solid was filtered, washed with THF
and dried under vacuum at 25°C.
Ir(C0)2Cl(p-toluidine)
8 2
A procedure reported by Klabunde u was used. In a
100 ml round bottom flask equipped with a reflux condenser
and a gas dispersion tube, 1.015 g IrCl,*3H?0, 0.290 g
anhydrous LiCl , 40ml 2-methoxyethano1 and 4.5 ml H?0 were
combined. The apparatus was purged with through the
gas dispersion tube for 15 minutes. The was switched
to CO and a slow bubble rate was maintained while refluxing
and stirring for 10 hours. The mixture was cooled and while
purging with N^, 0.377 g of p-toluidine was quickly
added. The mixture was stirred for 15 minutes and added to
145 ml of H^O. The purple precipitate was filtered in
air, washed with 90 ml 0 and dried under vacuum for 1
hour. The solution was filtered followed by removal of the
solvent under vacuum. Analysis: C, 30.12%; H, 2.53%; N,
3.90%; Theoretical: C, 27.92%; H, 2.24%; N, 3.35%.
(Silica Gel)\/\ P(Ph) 2Ir4(CO) n
The method used was derived from a preparation reported
7 9
by Schrader and Studer. In an inert atmosphere box in
a 500 ml Parr pressure bottle set-up (described in the
experimental section of Part Three) a degassed solution of
76.5 ml 2-methoxyethanol and 2.7 ml H^O was combined with

69
0.055 g Ir(CO)0C1(p-toluidine) , 18 g mossy zinc (acid
washed and chopped into small chunks) and the entire yield
of the resin resulting from the preparation of silica gel
ound phosphine silane ( 5 g). The system was pressurized to
40 psi ten times with argon followed by ten times with CO.
While stirring, the system was pressurized to 55 psi with CO
and heated to 90°C. (Note: Good stirring was essential to
obtain an active catalyst. A 1/2 inch star stir bar,
purchased from Fisher Chemical Co., worked well.) After 24
hours the system was cooled and the slurry was decanted from
the mossy zinc in air, followed by filtering. The yellowish
support was washed with THF and dried under vacuum for 24
hours at 25°C. (Heating while drying may result in
decomposition of the supported carbonyl cluster.) Analysis:
Ir, 0.23% (obtained by ICP).
(Silica Gel )-^^ P(Ph) 2lr4(CO) (High Loading)
The same procedure was used as above for
(silica gel) P (Ph) 21 r^ ( CO )^-^ except the pressure bottle
set-up was loaded with 0.110 g Ir(CO)2Cl(p-toluidine),
153 ml 2-methoxyethanol, 5.4 ml H^O, 36 g mossy zinc and
the entire yield from the preparation of high loading silica
gel bound phosphine silane. Analysis: Ir, 0.69%.

70
(Alumina )P ( Ph) 21 r 4( CO ) n
The same procedure was used as above for
(silica gel P (Ph) 2 I r^ ( CO ^ except the reagents
loaded in the pressure bottle set-up were: 3 g alumina bound
phosphine silane, 0.056 g Ir(CO)^C1(p-1oluidine) , 76.5 ml
2-inethoxyethanol , 2.7 ml H^O and 18.0 g mossy zinc.
Analysis: Ir, 0.75%: P, 0.84%. (The theoretical Ir^ : P
ratio is 1:27.)
Ir4(CO)i2 on Silica Gel (Physically adsorbed, 2.5% Ir)
The method used was derived from a preparation reported
8 3
by Howe. In a 100 ml round bottom flask, 2.0 g silica
gel (untreated), 0.072 g Ir^(C0)^2 and 50 ml cyclohexane
were combined. After stirring for 3 hours the solvent was
removed under vacuum and the resulting solid was dried for 6
hours at 25°C.
Ir4(C0)11P(Ph)3
The synthesis was derived from a preparation reported
84
by Shapley and Stuntz. In a 250 ml Parr pressure bottle
1 ml H^0 was combined with 30 ml 2-methoxyethanol. Carbon
monoxide was bubbled through the solution for 15 minutes by
way of a syringe needle. Quickly, 0.155 g (0.397 mmole) of
Ir(CO)2Cl(p-toluidine), 0.026 g (0.99 mmole) P(Ph)^,
3.0 g mossy zinc (acid washed) and a stir bar were added. A
pressure head was placed on the bottle and the system was

71
purged with 60 psi CO ten times. Under 60 psi CO, the
mixture was heated while stirring to 90°C. After 30
minutes the mixture was cooled, the pressure released and
the mixture filtered. The yellow filtrate was evaporated to
dryness under vacuum.
The residue was dissolved in 50 ml of 5:1
hexanes:methylene chloride solution and added in portions to
a 14" long, 1/2" diameter column packed with 230-400 mesh
silica gel. The yellow solution separated into two yellow
bands upon elution with 5:1 hexanes:methylene chloride.
Each band was collected and the solvent was removed under
vacuum. The first band off the column yielded a yellow
crystalline solid, Ir^(CO)^(Ph)^, and the second
band yielded a yellow oil IrCO)^Q(P(Ph)^^.
Infrared analysis of both compounds matched well with
4 8
literature reported spectra.
(OEt)3Si(CH2)2P(Ph)2Ir4(CO)n and
[(OEt)3Si(CH2)2PCPh)2]2lr4^CO)Mixture
The preparation used was reported by Schrader and
7 9
Studer. In an inert atmosphere box in a 500 ml Parr
pressure bottle, a degassed solution consisting of
100 ml 2-methoxyethanol and 3.2 ml 0, 0.20 g
IrCl(CO)^(p-toluidine ) and 4.5 g mossy zinc (acid
washed) were combined. A pressure head was placed on the
bottle and it was purged with 40 psi ten times with argon
followed by ten times with CO. Under 55 psi of CO the

72
system was heated to 90°C while stirring. After 12
hours the mixture was cooled, brought into an inert
atmosphere box and filtered. The solvent was removed from
the filtrate under vacuum. The IR spectrum of the
resulting yellow residue showed characteristic IR bands
for both iridium silane complexes. No separation was
attempted.
(Alumina) P ( Ph) 2 I r Cl ( CO) P ( Ph)3
The procedure used was derived from a preparation
8 5
reported by Evans et al. In a 100 ml round bottom
flask, 0.11 g of I r (CO) Cl (P (Ph) , 1.0 g alumina bound
phosphine silane and 55 ml benzene (dried over CaH-, and
distilled) were combined. After the mixture was stirred at
ambient temperature for 72 hours under , the support was
filtered, washed with benzene and dried under vacuum.
IrCl(CO)(P(PIO3)2 on Alumina (Physically adsorbed)
In a 100 ml round bottom flask, 0.11 g Ir(CO)Cl(P(Ph)^)^,
2.0 g alumina (acid washed) and 50 ml benzene were combined.
After stirring at ambient temperature for 120 hours under
, the solvent was removed by vacuum. The support was then
dried under vacuum for 12 hours.

73
Pyrolyzed RhftCCO)]^ on ZnO (0.6% Rh)
The preparation used was reported by Ichikawa.^^ In
a 300 ml round bottom flask, 0.042 g Rh^CCO)^^, 4.0 g
ZnO and 200 ml acetone were combined. The mixture was
stirred under for 24 hours and then the solvent was
removed under vacuum. The resulting solid was placed in a
glass tube and heated to 160°C under vacuum for 2.5 hours.
Results and Discussion
Polymer Supported [Ru(CO)3I3]" and [HRujC CO ) \ \ ] ~
Synthesis and characterization
The support used to attach the ruthenium anions
[Ru(C0)^Ij]~ and [HRu^(CO)^^]” was an ami nopropylsi1 ane
functionalized silica gel*' that had been modified to a
7 8
trimethylpropylammonium iodide form. The synthetic
procedure for this support is shown in Figure 3-2.
Having a sufficient concentration of quaternary
ammonium iodide groups on the silica gel surface was an
important consideration. This would allow the ruthenium
anions to interact with one another once ion exchanged onto
the support. The ruthenium anion interactions are suspected
6 7
to be important because in Dombek's0 homogeneous system
both anions had to be present in solution for catalysis and
neither anion was a good CO reduction catalyst.

Figure 3-2. Synthetic route for the preparation of
trimethylpropylammonium iodide functionalized
silica gel.

75
Step 1
j
i OH + (OEt)3Si-^s/>NH2 Toluene .
Step 2
\
O-Si^v^NH
/
2
+
CH31
DMF
\
O—Si'^V/v^NH9
/ ¿
Í
0-Si^v^n(cH3)3I

76
Based on an infrared study, Nyberg and Drago
8 7
reported that the concentration of organosulfide groups
needed on a silica gel support to allow the formation of the
rhodium carbonyl dimer shown below was 0.20 mmole S per gram
of silica gel.
Elemental analysis of the quaternary ammonium iodide
modified support showed that the support contained 8.37%
iodine which translates theoretically to 0.63 mmole
quaternary ammonium iodide groups per gram of silica gel.
Thus the concentration of quaternary ammomium iodide sites
should be more than sufficient to allow site interaction.
The anions [Ru(C0)jI^]" and [ HRu^( CO ) ^ ]
were first synthesized separately as shown by Equations 10
and 11, and isolated as the cesium and tetraethylammonium
salts respectively.
CsCl
RuI 3 + HI + HC00H > >Cs [Ru(CO ) 3I 3 ]
reflux
(10)
THF [NEt4]Br
Ru3(C0)12 + Na [ BH4 ] >
*[NEt4][HRu3(C0)n] (ID
2 5°C

77
A successful method for ion exchanging the two
ruthenium anions onto the support utilized two separate ion
exchange reactions in tetrahydrofuran. In the first ion
exchange reaction, the modified silica gel support was
stirred in a Cs[Ru(C0)-I^] THF solution which contained
a quantity of [Ru(CO)^I^] ions equal to one half the
number of theoretically available quaternary ammonium iodide
sites. The infrared spectrum of the isolated support after
stirring for 10 minutes at 25°C showed no evidence of
[ Ru( CO I-. ] being present (Figure 3-3b). Stirring
the support for 15 minutes under reflux conditions resulted
in an infrared spectrum (Figure 3-3c) containing two fairly
intense bands at 2091 and 2021 cm ^ (Table 3-4). These
correspond well with the CO stretching bands observed at
2100 and 2027 cm ^ for the KBr spectrum of Cs[Ru(COI^]
(Figure 3-4a). (The 2027 cm ^ value is the average
frequency of the two close bands at 2033 and 2021 cm ).
The resulting [Ru(C0)^I,]~ exchanged support was then
contacted with degassed, intensely maroon colored THF
solution containing the dissolved salt [NEt^][HRu^(CO )^^].
After 10 minutes of stirring at 25°C the isolated support
contained three main infrared bands (Figure 3-4c) in the CO
stretching frequency; 2099, 2036 and 1987 cm ^. These
infrared bands correspond well with what would result from
adding together the two spectra of the separate anions. The
infrared result fairly conclusively shows that the modified
silica gel support contains both the anions [Ru(C0)^I^]

Figure 3-3. Infrared spectra in the range 2500-2600 cm"l
of a) (silica gel) N(CH3)3 I, (nujol mull);
b) [Rul3(C0)3]- exchanged at 25°C, (nujol
mull); c) [RuI3(CO)3]" exchanged at reflux
temperature, (nujol mull).

79
CM 1
2500
—I—
2000
—I—
1800
—I
1600

Table 3-4. Comparison of Infrared Carbonyl Stretching Frequencies of
Supported and Non-Supported Ruthenium Complexes.
Compound Environment
V C = 0 (cm-1)
1)
Cs [Rul3 C CO )3 ]
KBr
210 0(s) , 2033(S) 2021(g)
2)
[NEt4][HRu(C0)n]
CH3CN
2070(w), 2010(g), 1998(g), 1440(m)
[2075(vw), 2018(vs), 1985(g), 194S(m)]
3)
[RUI3 ( CO )3 ] “ on
nu j ol
2 0 91( vs ) , 2021(g)
(Silica Gel)'V'N(CH3)3 +
4)
[RuI3(C0)3]-+[HRu3(C0)n]"
nu j ol
2099(g) , 2036(Br) , 1987(Br)
on (Silica Ge 1N(CH3)3 +
a Johnson et al.^0

Figure 3-4. Infrared spectra in the range 2500-1800 cm
of a) Cs[RuI3(C0)5], (KBr);
b) [NEt4][HRu3(C0)11], (in CH3CN) ;
c) [Rul3(C0)3J“ and [HRu3(CO)i\]“
on (silica gel N(CH3) 3+ , (nujol mull).

82
2500 2000 1800
CM"

83
and [HRu^(CO)^] but the relative concentration of
each is unknown .
Catalysis
Approximately 0.5 grams of the ruthenium substituted support
was placed in a reactor tube in an inert atmosphere box, and the
tube was then placed in the flow reactor system described in the
experimental section. On passing a 3:1 H^rCO mixture through
the catalyst at atmospheric pressure and a flow rate of 10
cm'Vminute no products were observed at temperatures below
150°C. At 150°C a small amount of methane was detected along
with some C 0 ^, which is often produced as a byproduct of
methanation or Fischer-Tropsch by way of the water gas shift
reaction. On raising the temperature to 175°C there was little
or no increase in methane production.
Covalently Supported Ir4(C0)n
Synthesis
The method used to attach Ir^(CO)x (where x = 10
or 11) clusters onto the surface of silica gel or
alumina involved covalently bonding them to surface
bound phosphine silane groups. The synthetic procedure
used was derived from work published by Schrader and
79
Studer and is shown in Figure 3-5. The silane,
2-(diphenylphosphino)ethyltriethoxysilane was first bound to
the surface of the support by reaction of the ethoxy groups
on the silane with the hydroxyl groups on the support

Figure 3-
Synthetic route for the preparation of (silica
gel or aluminaÍNAP(Ph)2lr4(C0)ix-

85
Step 1
H 4- (OEt)3Si
P(Ph),
Benzene
D i oxane
2 Reflux
S \
)-Si^\^p(Ph) + 3 ETOH
/ 2
Step 2
CO
IrfCOj Cl (p-toluidine) — >
2 h2o
2-methoxyethanol
11

86
surface. The next step involved assembling the tetrairidium
clusters from the monomer Ir(CO)^C1(p-1oluidine ) during
covalent attachment to the surface bound phosphine groups.
Through a fairly extensive FTIR study of the metal loaded
79
silica gel Studer and Schrader demonstrated that the
primary species functionalized on the surface was a mixture
of the following two clusters, ~—PIr4(C0)^1 and
P2Ir4(CO)10-
It was found that complete mixing in the cluster
supporting step was an important factor in obtaining an
active catalyst. Attempts to double the synthesis procedure
(using 10 g of support) resulted in severe stirring problems
and thus an inactive catalyst.
The three primary catalyst formulations investigated in
this study are shown in Table 3-5 along with their elemental
analyses.
Infrared characterization
A fairly extensive Fourier transform infrared study was
7 9
conducted by Studer and Schrader on tetrairidium
clusters bound by 2-(diphenylphospho)ethy11riethoxysi 1ane
functionalized silica gel. The characteristic carbonyl
stretching bands reported for both the mono-phosphine
substituted (silica ge 1)P(Ph)?Ir^(CO)^ and the
diphosphine substituted (silica ge 1)(x/N P(Ph)^¿1r4^CO)^q
are listed in Table 3-6. Also included is a summary of

87
Table 3-5. Elemental Analysis of the Primary Catalyst
Formulations.
Catalyst Wt%
Ir P H C
1. (Silica Gel) Va P(Ph)2Ir4(C0)n
.23
2. (Silica Gel)\/'P(Ph)2Ir4(C0)11
.69 - 6.40 1.34
3. (Alumina) Va P(Ph)2Ir4(C0)n
.75 .84

Table 3-6. Infrared Spectra of Silica Gel or Alumina Bound Tetrairidium Clusters
and Molecular Analogs.
Compound Environment yCO (cm”-*-)
Cyclohexane 2082^, 2048s, 2013m
1869y^, 1 8 5 3 jvj, 1 8 2 9 ¡vj
Ir4(C0)nP(Ph)3
I r4(CO)i!P(Ph)3 a
Ir4(C0 ) ]_]_P(Ph) 3 on Alumina
(Silica)vAp(Ph)2Ir4(CO)n a
(Silica)(s/NP(Ph)2)2lr4(C0)10 a
( Alumina)(v/^ P(Ph)2)l,(2)Ir4(co )l1,(10)
(Silica) (Va" P(Ph) 2) i f (2 )Ir4(C0) n t (10)
ch2ci2
2 08 8M) 2056Vs, 2 0 20s
18 87y\i/, 1 84 7m, 1 8 2 5m
Nu j ol
2083w, 2 0 51s, 2019m
Wafer
2 0 9Ojvj, 2 061m, 2023m
1890yw, 1 825,vf, 1 835m
Wafer
2 074S, 2050vs, 2 017M
Diffuse
Reflectance
2114M , 2060m, 2004s
Nu j ol
2092sh> 2070Shj 2041s, 2005m
a Schrader and Studer.7^

89
spectra taken of the polymer bound tetrairidium clusters and
molecular analogs used in this study.
The majority of the spectra were taken on a Perkin
Elmer 283B grating spectrometer except for the spectra of
Ir^(C0)x (x=10 or 11) bound to phosphine functionalized
alumina. These spectra were done by Nicolet on a Nicolet
20DX FT infrared spectrometer, using the diffuse reflectance
technique.
Spectra obtained for silica gel bound tetrairidium
clusters at two different iridium concentrations, 0.23% and
0.69%, are shown in Figure 3-6. At the low iridium
concentration (0.23%) the carbonyl stretching frequencies
due to the tetrairidium cluster were almost
indistinguishable from the background. The infrared
spectrum of the 0.69% Ir support showed more pronounced
carbonyl stretching bands. However accurate measurement of
these bands was difficult due to the limitations of the IR
spectrometer. Therefore it was difficult to determine if
the tetrairidium cluster was mono or diphosphine
substituted.
The spectra taken on the analogous alumina system
(Ir = 0.75%) were more conclusive. Figure 3-7 (a,b) shows
the FTIR spectra of the phosphine silane supported alumina
and metal supported phosphine silane functionalized
alumina. The spectrum resulting from the subtraction of
spectrum (a) from (b) is shown in (c). The remaining three
bands, 2114, 2060 and 2004 cm ^ of the tetrairidium

Figure 3-6. Infrared spectra (nujol mulls) in the range
2500-1600 cm-1 of (silica gel)vAP(Ph)2Ir4(C0)n
a) 0.23% Ir; b) 0.69% Ir.

91
CM-1

Figure 3-7. Fourier transform infrared spectra in the range
4000-400 cm-l (diffuse reflectance) of
a) (Alumina)^ P(Ph) 2,
b) ( Alumina )v^P( Ph) 2I r 4( CO ) n , c) b-a.


94
cluster correspond more closely to the spectrum reported
for the monophosphine supported cluster,
(silica gel)vA P(Ph)2Ir4(C0)
Figure 3-8 shows the infrared spectrum of
Ir^(C0)^P(Ph), before and after physical adsorption
(spectrum a and b respectively) onto the surface of alumina.
The spectrum of the cluster in cyclohexane and the nujol
spectrum of the cluster on alumina correspond well with the
spectrum of the cluster in CH^Cl., reported in the
7 Q
literature (Table 3-6).
Catalysis
A summary of the products produced by the following
catalyst studies are shown in Table 3-7. The polymer
supported tetrairidium cluster catalyst was first
tested under conditions similar to those reported
by Coliman et al.7^ and Muetterties et al.^ for the
Ir^(CO)^2/AlCl^-NaCl system. In the gas flow system
described in the experimental section the reactor tube was
loaded with a physical mixture of 0.7 g of
(silica gel)P(Ph)2Ir4(CO^ (0.23% Ir), 8 g
A1C1, and 1.8 g NaCl. Syngas containing a 3:1 H?:C0
mixture was passed through the catalyst bed at slightly
above atmospheric pressure.
On heating the catalyst mixture to 145°C the polymer
became suspended in the now liquid 2:1 AlCl^-NaCl melt. A
GC trace of the effluent gas is shown in Figure 3-9. The

Figure 3-8. Infrared spectra in the range 2500-1800 cm“l
of a) Ir4(C0)i iP(Ph)3, (in cyclohexane);
b) Ir4(COiP(Ph)3, physically adsorbed on
alumina, (nujol mull).

96
CM-1
I — - * 1 < 1 + i 1 ♦ - « f * * 1
2500 2000 1800 1600
CM'1

Table 3-7. Product Produced on Exposure to 1:3 C0:H2-
Catalysts
2 5°C
Products
1 4 5 °C
1.
(SG)NAP(Ph) 2Ir4(C0)11 / AlCl3-NaClb
CH3C1
ch4,
C 2H 6 >
ch3ci
2.
Ir4(C0)! 2 / AlCl3-NaCl
N. A.
ch4)
c2h6>
ch3ci
3.
(SG)vAP(Ph)2Ir4(C0)11 / P(but) 4Br
N. A.
ch4,
c2h6
4.
(SG) / A1Cl3-NaCl
N. A.
N. A.
5.
(SG)Va P(Ph)2 / A1C13-NaCl
N. A.
N. A.
a N.A.
no activity. b SG = silica gel.

0.49
98
CH4
CH3CH3
CH^CI
A
1
r^-
cg
-t
CT)
CO
min.
â– +â– 
o
o
d
Figure 3-9. GC traces of the products produced from CO
and H2 by (Silica Gel)P(Ph)2Ir4(CO)i1
and AlCl3~NaCl at 25°C (attenuation = 1,
500 1 sample, Poropak Q). a) After 0.25 hr.
b) After 1.75 hr.

99
identified products observed were methane, ethane, and
chloromethane which are some of the same products observed
7 0
in the homogeneous Ir4(CO)^2/AlCl^-NaCl system.
While still hot and under 0^ free conditions the
molten AlCl^-NaCl was filtered through the frit in the
reactor tube leaving the silica gel support behind. The
resulting AlCl^-NaCl melt, which solidified at room
temperature, was transferred to another reactor tube and
tested for its CO reduction activity. The melt showed
similar activity and product selectivity. As a check, a
mixture of unsubstituted silica gel and AlCl^-NaCl was
tested and showed no catalytic activity.
Based on the above evidence, it appears that the
polymer supported tetrairidium cluster in an AlCl,-NaCl
rnelt solvent undergoes the phosphine exchange reaction with
CO shown in Equation 12 generating a homogeneous system
consisting of unsupported Ir^CCO)^ in molten AlCl^-NaCl.
CO
(Silica Gel )\A p(Ph) 2Ir4(C0) 11 KSilica Gel)VNP(Ph)2 +
AlCl3-NaCl Ir4(C0)12 (12)
1 4 5°C
Thus at melt temperatures there is no benefit in covalently
supporting the tetrairidium cluster as it quickly leached
off of the support.

100
However, below melting temperatures in this system
an interesting new observation was made. At 25°C ,
on passing 3:1 H^iCO syngas through the
(silica gel)P(Ph)2Ir4(C0)n + AlCl3-NaCl
physical mixture, CO reduction was observed to produce a
single product. This product has been identified using two
GC columns (Poropak Q and DEGA) and GC mass spectrometry
(discussed later) as chloromethane.
The production of CH^Cl decreased steadily with time
as shown in Figure 3-10 where the intensity of the GC peak
had greatly decreased after 1.75 hours on stream. The
unsupported cluster Ir4(C0)-^2 was tested under
conditions similar to those used for the polymer supported
cluster. A physical mixture of 0.05 g Ir4(C0)^2 with
AlCl^-NaCl was tested. No activity was observed below
melting temperature (75°C). At 75°C partial melting
occurred and intense GC peaks were observed for methane,
ethane, CH..C1 and some larger products at retention times
above 10 minutes.
The phosphine substituted support (no Ir present)
combined with AlCl^ was tested and found to also be
inactive for CH^Cl production. Thus the polymer supported
iridium cluster species is important in the chemistry
observed at 25°C.
(Silica gel)v^ P(Ph)2Ir4(C0)11 (0.23% Ir) was
tested in another polar melt salt, tetrabutylphosphonium
bromide (melting point 100-103°C). Passing syngas through

101
5 5>
o ^
mm.
GC traces of the products produced from CO
and Hi by (Silica Ge 1) P (Ph)2 I r4 ( CO )i \
and AlCl3-NaCl at 145°C (attenuation = 2,
500 1 sample, Poropak. Q) .
Figure 3-10.

102
a physical mixture of 0.7 g supported Ir^(CO)^^ and 4 g
tetrabutylphosphonium bromide resulted in no activity below
175°C. Above 175°C a small amount of methane and ethane
was observed along with some unidentified peaks at retention
times greater than 10 minutes.
CH^Cl catalyst development
The novel chemistry observed for the selective
production of CH^Cl by silica gel supported Ir^(CO)^
+ AlCl^ under mild conditions warranted testing its
potential use as a CH^Cl catalyst.
At 25°C a catalyst consisting of a physical mixture
of 0.7 g (silica gel)v^ P(Ph)2Ir4(C0)u (0.23% Ir)
and 0.1 g AlClj was exposed to 3:1 H^iCO gas. Methylchloride
activity was observed but it dropped off rapidly with time.
The addition of anhydrous HC1 to the feed gas, the feed now
approximately 3:1:0.8 H2:C0:HC1, resulted in restoration
of the initial CH^Cl activity. This cycle of loss and
gain of activity corresponding to the presence and absence
of HC1 in the feed could be repeated numerous times. The
loss of chlorine (the source being AlCl^) from the
catalyst mixture, which leads to rapid loss in activity, can
thus be counteracted by addition of HC1 gas to the feed.
Temporary exposure of the catalyst to 0^ after previous
exposure to the syngas-HCl feed resulted in permanent
deactivation of the catalyst.

103
6 9
The proposed role of AlCl^ in Muetterties' et al.
homogeneous system was to aid in the activation of metal
bound carbonyls to allow reduction by hydrogen under milder
conditions (shown below). Also, the AlCl^ provides a
chloride source for the minor production of CH^Cl.
M—C=0 • • *A1C13
It is believed that AlCl^ plays a similar beneficial
role in the polymer supported phosphine tetrairidium cluster
system. However, the presence of AlCl^ in the catalyst
formulation was detrimental to use of the catalyst at
elevated temperatures due to the low melting point of
AlClj. As demonstrated previously upon melting the
AlCl^, the attached cluster leached off the support
generating the non CH,C1 selective homogeneous system.
(Table 3-7, catalyst 1).
Both the silica gel functionalized and a similar
alumina functionalized phosphine tetrairidium cluster were
tested for their ability to convert syngas and HCl(g) to
CH^Cl in the absence of AlCl^. In both cases after an
initial 15-20 minute induction period, CH^Cl was observed
as the primary product at 25°C. Increasing reaction
temperature from 25°C up to 100°C greatly increased
catalyst activity while maintaining its selectivity for
CH^Cl . Figures 3-11 and 3-12 show the GC traces at

Figure 3-11. GC traces (Poropak Q) of the products produced
from syngas and HC1 by (Alumina)v^ PIr4(CO)^
at a) 50°C and b) 100°C.

105
4

Figure 3-12. GC traces (Poropak Q) of the products produced
from syngas and HC1 by
(silica gel)\APIr4(C0)11 a) .23% Ir, 25°C;
b) .23% Ir, 100°C; c) .69% Ir, 100°C.

107
2
4
4

108
select temperatures for the alumina and silica gel based
systems respectively.
In the two figures, the initial three peaks labeled 1,2
and 3 observed for the majority of the reported GC traces
correspond to CH^ , CH^CH^, and HC1 respectively. The
methane observed results from an impurity in the CO gas
source. The ethylene observed is an impurity found in the
HC1 source. The HC1 source also contains a slight ClLCH^Cl
impurity. As can be seen qualitatively, CH,C1 (peak 4)
is the principle product observed in both the silica and
alumina systems. The positively identified secondary
products designated by the numbers 5,6 and 7 correspond to
acetylaldehyde, methylformate and ethylchloride respectively
and are present in both systems although the relative
amounts vary. (Products were positively identified by GC
mass spectrometry, discussed later). The alumina catalyst
seemed to produce more ethylchloride relative to the other
minor products than the silica gel catalysts. Also, the
unidentified impurity between peaks 6 and 7 is slightly more
prominent in the alumina case. Comparison of a 0.23% Ir and
a 0.69% Ir silica gel supported catalyst shows no
significant difference in product selectivity as evidenced
by the almost identical GC traces at 100°C (Figure 3-12, b
and c).
The induction period observed before the appearance of
CH^Cl was probably due to the formation of surface
chloride species, resulting from the reaction of surface

109
hydroxyls with HC1 as shown in Equation 13. These surface
+ 3 HCI
Alumina or silica
+ 3 H20
(13)
Si-Cl or Al-Cl species could then act in a manner similar to
that previously proposed for A1C1, in aiding the reduction
of carbon monoxide.
The activities of various silica gel and alumina
catalysts at various temperatures for the production of
CH^Cl are listed in Table 3-8. The activities are based
on the rate of CH,C1 leaving the reactor and do not take
into account any deactivation which might have occurred over
the time the catalysts were tested. Comparison of the two
silica gel based catalysts containing 0.23% and 0.69% Ir
shows that increasing the metal loading on the support
results in an increase in the production of CH..C1 per gram
of catalyst. This increase in activity appears to be more
substantial at the higher reaction temperatures. The
alumina based catalyst which has the highest percent iridium
of the three catalysts listed, 0.75%, showed the highest
activity per gram of catalyst.
Table 3-9 illustrates the data in terms of the turnover
numbers of these same catalysts. The turnover number is
defined as the moles of CH^Cl produced per tetrairidium

Table 3-8. Chloromethane Activities Per Gram Catalyst.
CH3CI Activity3 (mole/sec • g catalyst)
Catalyst
2 5°C
5 0°C
7 5°C
100°C
1.
(Silica Gel)vAP(Ph)2Ir4(CO)11
3.4X10-11
2.5X10“10
4.6X10-10
1.5X10 " 9
(Ir = .23%)
2.
(Silica Gel)vAP(Ph) 2Ir4(C0)11
8.6x10 -n
4.6X10-10
1.6X10-9
7.7X10"9
(Ir = .69%)
3.
(Alumina)Va P(Ph)2lr4(C0)^]_
-
6.4X10 " 1 0
2.6XIO-9
1.1X10’8
(Ir = .75%)
3 Exit gas flow rate .02 - .04 ml/sec.
110

Table 3-9. Turnover Rates of CH3CI Per Tetrairidium Cluster.
Turnover
2 5°C
# (molecules
5 0°C
CH3Cl/1r4 •
7 5°C
Sec)
100°C
1.
(Silica
Gel )\/vP(Ph) 2Ir4(C0) n
1.13X10”5
8.33X10'5
1.53X10-4
5.00X10-4
(Ir
= .23%)
2.
(Silica
Gel)vAP(Ph)2Ir4(C0)n
9.5 8X10“6
5. 13X10"5
1.78X10-4
8.58X10-4
(Ir
= .69%)
3.
(Alumina)vAP(Ph)2lr4(C0)n
-
6.55X10-5
2.70X10"4
1.17X10-3
(Ir
= .75%)
Ill

112
cluster per second. A plot of turnovers vs. temperature for
the catalysts is shown in Figure 3-13.
Comparison of the 0.23% and 0.69% silica gel catalysts
showed that at 25°C and 50°C the 0.23% Ir was more
active per metal cluster. At higher temperatures, 75°C
and 100°C, the 0.69% Ir catalyst becomes more active than
the 0.23% Ir catalyst. The alumina catalyst, which had an
even higher iridium concentration (0.75%), had a turnover
number at 50°C between the two silica gel catalyst
values. However, at 75°C and more so at 100°C this
catalyst was the most active per tetrairidium cluster.
It is difficult to place a high level of confidence in
the differences observed in the activities of these
catalysts. This is due to the substantial error introduced
in the activity measurements especially at lower
temperatures. But if the differences can be believed at
higher temperatures it appears that in the concentration
range studied the activity for the production per metal
cluster increases with metal loading.
The differences observed may be due to many factors
other than metal loading, such as support interactions,
concentration of phosphine on the surface, and deactivation
processes all of which need to be explored further.
Based on the results to date, chloromethane appears to
be the primary product of this catalytic reaction, though
total confidence cannot be placed in this statement without

Figure 3-13. Plot of turnover number versus temperature
for both silica gel and alumina supported
tetrairidiurn cluster catalysts.

TURNOVER #/SEC x 10"
114
m
o

115
a proper material balance which was not possible with the
current experimental setup.
The rate of CH^CH^Cl production by the alumina
supported catalyst at 100°C was estimated to be on the
order of 4 x 10 11 mole/sec- g of catalyst. Based on the
assumption that the production of the other impurities
observed was similar to CH^CH^Cl, the selectivity toward
the production of CH^Cl was calculated to be greater than
9 9%.
A byproduct observed condensing at the top of the
reactor tube for both the silica gel and the alumina
catalysts was H^O. No detectable quantity of CO^ was
observed being produced indicating that all of the carbon
monoxide oxygen (except for the small amount of oxygen
contained in the minor products) was going into the
production of H^O. GC analysis of a H^O sample using a
TC detector and a DEGA column showed the presence of two
unknown high molecular weight and/or polar compounds at
retention times 4.16 and 6.07 minutes (Figure 3-14). No
such compounds were observed with the alumina catalyst.
Qualitatively, the rate of production of CH^Cl
appeared stable at temperatures less than or equal to 75°C
for these tetrairidium supported catalysts for weeks. At
100°C there was some catalyst deactivation with time. One
factor that was observed to affect catalyst stability was
the concentration of unreacted HC1 gas leaving the reactor.
If the HC1 gas in the feed was adjusted to minimize HC1 in

116
GC traces of the products present in the
water produced from syngas and HC1 by
(Silica Gel)v^P(Ph)2Ir4(CO)11 (.23% Ir)
at 80°C (attenuation = 1, DEGA column).
Figure 3-14.

117
the exit gas, the catalyst qualitatively appeared more
stable. The amount of HC1 in the exit gas was monitored by
GC.
Prior to exposure to HC1, the catalysts are stable to
air at room temperature. Once exposed to HCl-syngas,
subsequent exposure to oxygen renders the catalyst
inactive. This indicates the active catalyst species, or an
intermediate species in the catalytic cycle, is oxygen
sensitive unlike the catalytic precursor.
Table 3-10 lists the experimental results for a number
of different systems tested for catalytic activity. These
were designed to help understand what property(s) are most
important to the catalytic activity of the silica gel and
alumina covalently supported tetrairidium cluster catalyst.
A catalyst of physically adsorbed Ir^CCO)-^
(2.5% Ir) on silica gel was found to be inactive for the
production of CH^Cl from syngas and HC1 up to 100°C.
Based on the GC retention time a small amount of what was
believed to be CH^CH^Cl was observed being produced at
80°C. On heating to 150°C the light yellow catalyst
turned grey (indicating decomposition to iridium metal)
followed by production of a small amount of CH^, CH^Cl
and other higher molecular weight hydrocarbons. This
result, along with the observation discussed earlier that
Ir4(CO)^2 + A1C1, does not produce CH^Cl at low
temperatures, illustrates the importance of the substituted

Table 3-10. Qualitative Activities Observed for the Production of
CH3CI from Syngas and HC1.
Catalyst
Activity 100°C
Ir4(C0)42 on Alumina (2.5% Ir)
inactive
(0Et)3Si P(Ph)2Ir4(C0)n
and + AICI3
[(0Et)3Six^ P(Ph)2]2Ir4(C0)10
slight activity
Ir4(C0)11P(Ph)3 + AICI3
inactive
Ir4(CO)4iP(Ph)3 on Alumina
inactive
Ir(CO )C1(P(Ph)3)2 on Alumina
inactive
(Alumina) vA P(Ph)2Ir(CO)C1P(Ph)3
slight activity
Rh6(C0)x6 on ZnO (pyrolyzed)
inactive
118

119
phosphine and/or the phosphine silane linkage to the
clusters catalytic activity.
The compounds (OEt)i \,A P(Ph)^IrCO)^^ and
[(OEt)^Si P(Ph)?]r4(C0)^0 which are believed
to be the molecular analogs of the supported clusters, were
7 9
synthesized and tested for CH^Cl activity. The
material isolated from the preparation consisted of a
mixture of the two complexes and 0.1 g of this material was
mixed with 4.0 g AlCl^ in an inert atmosphere. On
exposure to syngas and HC1 at 25° C, this solid catalyst
showed slight activity for CH^Cl.
A similar molecular analog was tested,
I(COP(Ph) which contained P(Ph)^ instead of a
phosphine silane group. This was mixed with AlCl^ (O.Olg
Ir4(CO)^^ P(Ph).., 3.5 g AlClj) and showed no
production of CH^Cl at 25°C. When the temperature was
increased, the production of CH^Cl was observed along with
production of CH^ indicating that partial melting of the
A1C1, may have occurred.
The monophosphine complex Ir^(CO)^^P(Ph)^
physically adsorbed onto alumina was also tested for its
CH^Cl activity. As seen in the previous test
( Ir4(C0)j, 4P(Ph)^ mixed with AlCl^) no CH^Cl
production was detected on exposure to syngas and HC1 at
25°C. No products were observed up to 100°C. At
100°C, a small amount of CH^Cl was observed along with

120
CH^. Problems with isolating I r CO ) ^ Q( P ( Ph) ^) , during
synthesis prevented testing it for catalytic activity.
The results of the molecular analog tests illustrated
that the role of the covalent linkage to the phosphine
silane may be important to the low temperature production of
CH,C1. The inactivity of the monophosphine cluster
P(Ph)^lr^(CO)ii for production of CH,C1 at 25°C
could be explained in a number of ways: 1) as well as
supplying a phosphine ligand, the phosphine silane may be
playing an additional role in the chemistry, 2) the
diphosphine substituted cluster might be the active species
and 3) there may be enough of a difference in the electronic
properties of the silane phosphine and P(Ph)^ to alter the
chemistry.
In an attempt to illustrate that an iridium cluster is
needed to facilitate the low temperature reduction of CO to
CH-C1, a supported iridium monomer was tested. The
monomer chosen was Ir(CO)Cl(P(Ph)^^, Vaska's complex.
The choice was based on the fact that its ligand environment
about the iridium atom is similar to what might be expected
for an iridium atom in the active supported cluster
catalyst. Also the Vaska complex is well known for its
ability to oxidatively add and HC1.
Ir(CO)Cl(P(Ph) , )^ was supported on alumina by two
methods. The first method involved physical adsorption onto
unfunctionalized alumina. The second made use of covalent
linkage to a phosphine silane functionalized alumina, taking

121
8 5
advantage of the phosphine exchange reaction shown below
(Equa tion 14).
Siv^PÍPh^ + Ir(CQ)Ol(P(Ph},>
3'2
"Si sA P(Phj^Ir(CO)C I P(P^
P(PhL
(14)
On exposure to syngas and HC1 the physically adsorbed
Ir(CO)Cl(P(Ph)j2 showed no activity at 25°C. After
increasing the temperature to 50°C, the only product
observed was CH^CH^Cl. It was not until 100°C had
been reached that any CH^Cl production was observed (see
GC traces in Figure 3-15).
GC traces of the products observed for the covalently
attached Ir(CO)C1P(Ph)^ are shown in Figure 3-16. Unlike
the physically adsorbed catalyst slight CH^Cl activity was
observed at 25°C. Increasing the temperature to 75°C
greatly increased CH^Cl production. However this
production level was very low compared to that observed for
the Ir^(CO)^(Ph)^'— supported cluster catalyst.
Again it appears that the covalent phosphine linkage is
important for CH^Cl activity. The iridium monomer did
show CH^Cl activity at 25°C but in no way compared with
the activity of the iridium cluster catalysts. This

Figure 3-15. GC traces (Poropak Q) of the products produced
from syngas and HC1 by IR(CO)Cl(P(Ph)3J2
physically adsorbed on alumina at a) 50°C
b) 100°C.

123
2
2 3

Figure 3-16. GC traces (Poropak Q) of the products
produced from syngas and HC1 by
(Alumina)P(Ph)2Ir(CO)C1P(Ph)3 at
a) 2 5° C b) 7 5°C.

125
gH
i CHoCl
i r
23
g,L
Att.*4
T
Att. = 4
CH3CH2C!
co
o
CD
â– 'T
min.

126
illustrates the importance of the role of a multimetal
cluster in this type of chemistry.
To help demonstrate the uniqueness of the chemistry
shown by these covalently supported tetrairidium clusters,
8 6
a methanol catalyst reported by Ichikawa was tested for
its ability to convert syngas and HC1 to CH^Cl. The
catalyst was composed of pyrolyzed Rh^(CO)^ on ZnO, and
is known to produce methanol from syngas under mild
conditions (220°C, 45 cm Hg). On exposure to syngas and
HC1 , the catalyst showed no CH^Cl production activity up
to 80°C. At 80°C a small amount of CH^Cl and CH,OH
was observed. Increasing the temperature further only
slightly improved the CH^Cl activity but other products
such as CH^ were also produced.
Halogen sources
Other halogen sources besides HC1 tested in
conjunction with syngas with these tetrairidium supported
catalysts were HBr, aqueous HC1 and Cl^ gas.
At 100°C while passing syngas and HCl(g) through a
silica gel supported catalyst (0.23% Ir) the HC1 was
replaced in the feed by HBr(g). Before HBr was introduced
into the feed, HC1 free syngas was passed through the
catalyst until almost no CH^Cl product was observed in the
exit gas. Figure 3-17 contains GC traces which illustrate
the progression of products as a function of the time that
the HBr was present in the feed. After 1/2 hour, the

Figure 3-17. GC traces (Poropak Q) of the products
produced from syngas and HC1 by
(silica gel )\/s P(Ph) 2^4(00 ) n (.23% Ir)
at 100°C on introducing HBr for a) 0.0 hrs
b) 0.5 hrs c) 1.5 hrs d) greater than 10 hrs.

128
CHUCI
a .JL_LL
HBr Present
0.0 hr
0.5 hr
1.5 hrs
>1 0.0 hrs
0
5
m i n
10
15

129
primary product observed was CH^Cl and the beginning of
CH^Br production was observed. (CH^Br was identified by
GC-mass spectroscopy discussed later). A small peak at the
retention time of ethylchloride was also observed. After
1.5 hours, the production of CH,Br appeared greater than
CH.J.C1 , and the appearance of unknown minor products above
the retention time of CH^CH^Cl were detected. Finally
after a period greater than 10 hours the sole primary
product was CH^Br and there was almost no trace of
CH^Cl. However a minor product at a retention time of
about 15 minutes was still present which could be
ethylbromide though there has been no positive
identification.
On changing the HBr in the feed back to HC1, it was
observed that the catalyst was nearly inactive as it
produced only very small amounts of CH^Cl. Thus this
catalyst can produce CH^X selectively using at least two
different hydrogen halide sources, HC1 and HBr. These
results also demonstrate that the catalyst can be converted
from a CH^Cl to CH^Br producing catalyst but not in the
reverse order. The production of CH^Cl a short time after
introducing HBr into the feed demonstrated that a
significant amount of Cl remained inactive on the
catalyst, probably in the form of Si-Cl groups which became
active in the presence of HBr.
An experiment similar to that described above was
performed using an alumina supported iridium cluster

130
catalyst at 100°C, except in this case anhydrous HC1 was
replaced by aqueous HC1 as opposed to HBr. The catalyst was
first made active using anhydrous HC1. Then the HC1 was
removed until almost no CH-^Cl production was observed. To
introduce the aqueous HC1 a stream of argon gas, passed
through a gas dispersion tube submerged in concentrated
hydrochloric acid, was used. The resulting argon-HCl(aq)
gas was then mixed with 3:1 H^iCO syngas and passed
through the catalyst. After 15 minutes the catalyst showed
good activity for producing CH,C1. After 1 hour the
activity was at a maximum and proceeded to decrease with
time. This indicated that the catalyst may not be stable to
a feed gas with a high water vapor content, and/or the
decrease in activity results from the decrease in the
concentration of HC1 in the aqueous solution. The
concentration of HC1 in concentrated hydrochloric acid
starts at 38% HC1. As the argon gas is passed through, this
concentration will eventually drop to 20% which is the
HC1 H^O constant boiling azeotrope. Further study is
needed to determine if the CH^Cl activity levels out with
time.
Preliminary results were obtained on a parallel
experiment using C1 ^ as the chlorine source. When C 1 ^
was introduced to an alumina catalyst under the same
conditions as described above, activity for CH^Cl was
observed but at levels lower than for either HCl(g) or

131
HCl(aq). Further studies with Cl7 were hindered due to
lack of time.
GC-Mass spectrometry
Volatile products obtained from the reaction of
syngas and HX (X=C1, Br) over the catalyst
(silica gel)vA P(Ph)2Ir^(CO^, where Ir= 0.23%,
were analyzed by GC mass spectrometry. The products were
collected over a 24 hour period in a CO^/acetone trap at
the exit of the reactor tube.
For the HC1 case the GC trace obtained is shown in
Figure 3-18. The mass spectra of peaks A, B, and C are
shown in Figures 3-19, 3-20, and 3-21 and are compared to
8 8
literature reported spectra. Peak A, the major
component, was CH^Cl. The peaks B and C correspond to
acetylaldehyde and methylformate respectively. The peak
labeled D has the same retention time as ethylchloride but
was not identifiable by mass spectrometry. Subsequent
89
investigations have positively identified peak D as
ethylchloride.
When HC1 was replaced by HBr in the feed gas the
volatile products that were trapped are shown in the GC
trace in Figure 3-22. The mass spectrum of peak E, which
represents the major component, CH^Br, is shown in Figure
8 8
3-23 compared to its literature reported spectrum.
Peak F was unidentifiable, but because it has a retention

132
Figure 3-18. GC traces (Poropak Q) of the products
produced from syngas and HC1 by
(silica gel)vA P(Ph)2Ir4(C0)11 (Ir = .23%)
at 75° and analyzed by GC mass spectrometry.

Figure 3-19. Mass spectrum of CH3CI, peak A (Figure 3-18),
a) observed spectrum b) literature reported
spectrum .®8

134
i ee se

Figure 3-20. Mass spectrum of acetylaldehyde, peak B
(Figure 3-18), a) observed spectrum
b) literature reported spectrum.^8

136
IBB
10 ?0 30 *0 60 *0 70 «0 »0 100 110 120 113 1*0 150

Figure 3-21. Mass spectrum of methylformate, peak C
(Figure 3-18), a) observed spectrum
b) literature reported spectrum.88

138
180 31

139
O 5 10
min.
Figure 3-22. GC traces (Poropak Q) of the products
produced from syngas and HBr by
(Silica Gel )>A P (Ph) 2I r4C0 ) i x (Ir = .23%)
at 100°C and analyzed by GC mass spectrometry.

Figure 3-23. Mass spectrum of CHjBr, peak E (Figure 3-22),
a) observed spectrum b) literature reported
spectrum .^ ^

141

142
time similar to that of ethylchloride, it is believed to be
ethylbromide.
Mechani sin
The mechanism for the novel chemistry demonstrated by
these covalently supported tetrairidium clusters may only be
speculated about at this point. Figure 3-24 shows one
possible reaction pathway based on some already established
organometal1ic chemistry.
One of the first steps toward the production of CH,C1
that might be envisioned is the oxidative addition of
generating a dihydride (1). Because the covalent attachment
of the phosphine silane to the cluster appears to be
necessary for catalytic activity, it may be that the iridium
atom directly bound to the phosphine is involved in the H0
activation. This is because the iridium bound directly to
the phosphine is predicted to be more electron rich than the
other iridium atoms in the cluster.
Interaction of the dihydride with the support surface
consisting of A-Cl groups (A = A1 or Si) could induce rapid
hydride migration forming the formyl type intermediate
(2). This reaction step is modeled after the reaction
9 0
reported by Shriver et al. (Equation 15). The rate of
CO insertion (alkyl migration) into a metal alkyl bond was
shown to be increased by CO interacting with the Lewis acid
AlBr^ generating a stable metal acyl complex. Stable

Figure 3-24. Speculative mechanistic scheme for the
production of CH3CI from syngas and HC1 by
polymer supported Ir^CO)]^.

H
/
CH3- O/..
'A—Cl
HCI
CH3CI
+ H20 + A—Cl
H,
Route 2
7
P-M-CO
A —Cl
H
P~K .H
c
c; a
HCI
H,
Route 1
ch3ci
A-CI + H20
IHCI
+ HOA
^HCI
H
-P-M + CH3OA
Cl
H
-P - M — C — Ó-A
1 1
Cl H
144

145
metal formyl formation was not achieved using the metal
hydride.
CH3
(CO)^Mn + AIBr^ —
Nco
At this point in the catalytic cycle, the second
hydride transfer can be invisioned to occur by one of two
routes. In the first route, the second hydride is
transferred to the formyl carbon along with the concerted
formation of a A-0 and a M-Cl bond, generating intermediate
(3). This intermediate activates H0 generating the
dihydride (4) which on hydride transfer to the metal bound
methoxy-A generates CH^OA and intermediate (5). The
methoxy-A group then can react with HC1 producing CH^Cl
and A-OH which on reaction with another molecule of HC1
would be converted back to A-Cl. The hydride intermediate
(5) can react with giving a metal dihydride (6) which
upon bonding a CO results in the formation of intermediate
(1) again.
The other route (route 2) forms a bound formaldehyde
type intermediate (7) on transfer of the second metal
hydride to the formyl intermediate (2). Similar reduction
eliminations of a formyl group to form a bound formaldehyde
have been proposed in the past.^^ On addition and
CH-
(CO),} Mn—,C’/
Br P
naiX
/ \
Br Br
(15)

146
transfer of another molecule a Lewis acid bound
methanol molecule and intermediate (8) are formed. The
bound methanol can then react with a molecule of HC1
generating CH,C1 and 0. Intermediate (8) can then
bind a CO molecule closing the catalytic cycle.
The formation of the minor products, acetylaldehyde and
CH^CH^Cl which contain C-C bonds probably proceeds
through a CO insertion step involving one of the
intermediates in the catalytic cycle. Another potential
source of ethyl chloride could be from a metal catalyzed
reaction of ethylene with HC1, the source of ethylene being
an impurity in the HC1 gas source.
Conclusion
The main goal of this study was to immobilize known
homogeneous CO reduction catalysts geared toward developing
catalysts capable of selectively producing chemicals from
syngas under very mild reaction conditions.
Two catalyst systems were studied. The first involved
the ionic attachment of two ruthenium anions
[Ru(C0)^Ij] and [HRu^(CO)^] simultaneously on
ammonium iodide functionalized silica gel. The ions were
successfully attached to the support as evidenced by
infrared spectroscopy but showed little or no syngas
conversion up to 175°C.

147
The second system involved the covalent attachment of
Ir^CCO)-^ to both phosphine silane functionalized silica
gel and alumina. This catalyst, in conjunction with
AlCl^-NaCl under melt conditions ( 140°C), demonstrated
no significant benefits over Meutterties' homogeneous
Ir4(CO ) ^/AlCl ^-NaCl system. The polymer supported
P(Ph)^Ir^(COunderwent an exchange reaction with CO
generating what was believed to be a homogeneous
Ir4(C0)^2/AlClj-NaCl system.
At 25°C in the presence of AlCl^ under non-melt
conditions the supported tetrairidium catalysts were found
to produce CH,C1 selectively from syngas. The AlCl^ was
successfully replaced in both the alumina and silica gel
system by the addition of HC1 to the syngas feed. This
allowed the operation of the catalyst at a higher
temperature, up to 100°C, while still maintaining a
greater than 99% selectivity for CH^Cl.
The presence of a Lewis acid, either AlCl^ or the
Lewis acid sites on the support surface, as well as the
phosphine silane linkage to the surface appear to be
important to the catalysts' activity. Although a phosphine
silane iridium monomer catalyst precursor, Ir(CO)ClP(Ph)^,
showed slight CH,C1 activity, the bound tetrairidium
cluster was superior.
The chemistry was also demonstrated using other halogen
sources, aqueous HC1, HBr, and Cl^. In the case of HBr
the primary product was CH^Br.

148
The polymer supported tetrairidium cluster system has
demonstrated novel, selective chemistry for the production
of methyl chloride under very mild conditions. This system
not only demonstrates some of the potential advantages of
"hybrid" type catalyst systems but has the potential for
9 2
being an industrially important process for the
production of CH^Cl from syngas and HC1.

IV. IMIDAZOLE FUNCTIONALIZED SILICA GEL
Introduction
The ligand imidazole or the deprotonated form,
imidazolate are of interest because of their role in the
93-98
active sites of many biological systems as well as
2 3
their involvement in homogeneous catalysis. ’
f=\
Imidazole (ImH) Imidazolate (Im)
9 9
The metaloenzymes carbonic anhydrase, carbonyl
peptidase, *^ thermolysin,^^1 and bovine erythrocyte
10 2
superoxide dismutase, all have been found to contain
imidazole in some form in their transition metal binding
sites. In the case of carbonic anhydrase, which catalyzes
the reaction of CO^ to HCO^-, Zn(II) is believed to
be bound in the active site by three imidazole rings of the
enzyme's histidine residues. Studies on an active form of
bovine erythrocyte superoxide dismutase has revealed an
9 3
imidazolate bridged copper (II) active site.
149

150
Imidazole's role in homogeneous catalysis was revealed
2 3
by two Japanese patents ’ in which a rhodium imidazolate
triiner [Rh(Im)C0D]^ (COD = cyclo-octa-1 ,5-diene) was
reported as an active catalyst for the hydroformylation of
terminal olefins (Equation 1)'.
. 0
R-C = C + CO + H? catalyst R-CH7CH?C^ (1)
* XH
The proposed structure of the catalyst precursor is shown
below. A study of similar polynuclear rhodium and iridium
complexes of the formula [M(RIm)(diolefin) ] (R = H, 2-Me)
reported by Tiripicchio and Uson.'*'^ Molecular weight
measurements determined that x was equal to a value between
2 and 3. A crystal structure of [Rh(2-MeIm)(CO^] which
was easily obtained from the diolefin complex was found to
have a structure similar to that shown above, but the
complex was a tetramer (x=4).
Reported in this study is the synthesis of an imidazole
functionalized silica gel support that has the potential to

151
form these rhodium imidazolate polynuclear complexes on the
surface of silica gel. A heterogenized rhodium imidazolate
catalyst will hopefully mimic the activity of the
homogeneous system while maintaining some of the advantages
of a heterogeneous system pre'viously discussed in the
introduction to chapter 3 (i.e. ease of catalyst separation
from product, greater solvent variability).
The following considerations were taken into account
when designing the imidazole support. First, there needs to
be sufficient surface coverage of the imidazole groups to
allow the polynuclear complexes to form. Second, the groups
connecting the imidazole to the silica gel surface should be
flexible and long enough to allow the imidazole to obtain
the necessary orientations. Finally, the synthesis of the
functionalized support should be relatively uncomplicated.
One of the most popular, and flexible methods of
functionalizing silica gel has been by using
organosilanes.'*'^’A method reported by Burwel l10 ^
for synthesizing an imidazole functionalized silica gel
using organosilanes is shown in Equation 2. In this method
the imidazole silane was synthesized on the silica gel
surface by reacting imidazole with a chloropropy1silane
functionalized support. The major problem with using this

152
imidazole support is that it lacks bridging capabilities due
to the imidazole ring being attached to the organic chain
through one of the ring nitrogens. Burwell reported
attempting the synthesis of the 4(5) substituted
i mi dazoly1si1ane below which would have the potential to act
as a bridging ligand, but the synthesis was unsuccessful.
Reported here is a convenient method for the synthesis
of a 4(5) substituted imidazolylsilane functionalized silica
gel utilizing a series of simple Schiff base reactions.
This support was then reacted with Rh(COD)(acac) in an
attempt to generate a functionalized rhodium imidazolate
polynuclear catalyst. The catalyst was then screened for
its hydroformylation activity.
The hydroformylation or 0X0 reaction (Equation 1) has
been the subject of extensive study.^m The early
commercial processes involved homogeneous cobalt carbonyl
catalysts operating at 150°C and 180°C and pressures of
200 to 400 atm. The active catalytic species was believed
to be HCo(CO)^. The traditional cobalt catalysts have
been replaced by more selective and active rhodium systems.
These operate at 100°C and pressure of 100 to 300 psi and

153
are generally of the form L^RhCCO^H (L = trialkyl or
triaryl phosphines).
Improved catalyst systems should demonstrate high
activity under mild reaction conditions, low by-product
production and show a high selectivity toward normal
aldehydes vs. isoaldehydes, which have little commercial
value. The commercial rhodium^^ systems are 10^ times
more active than the cobalt catalyst systems and demonstrate
normal to isoaldehyde ratios of 8-16:1 vs. 3-4:1 for the
cobalt case. Another important property should be easy
product separation with minimal catalyst loss.
Experimental
Materials
All solvents and reagents were used as purchased unless
otherwise stated. Triethoxypropylaminosilane was purchased
from Petrarch Chemical. The complex [RhCl(C0)2]? was
purchased from Alfa. Silica gel was purchased from W. R.
Grace and was Davison grade #62. The wide pore diameter was
14 mm, pore volume was 1.1 cm^/g and had a specific area
of 340 m^/g.
Instrumentation
Elemental analyses were performed by the
Microanalytical Laboratory, University of Florida,

154
Gainesville, Florida. Infrared spectra were recorded as
Nujol mulls on a Perkin Elmer 2 83B spectrometer. GC
analyses were performed on a model 3700 FID Varian gas
chromatograph equipped with 1/16" X 1 m stainless steel
column packed with Chromasorb P supported diethylene glycol
adipate.
Hydroformylation reactions were performed in a 500 ml
Parr pressure bottle containing a teflon coated magnetic
stir bar. The bottle was sealed with a silicone rubber
stopper fitted with a brass gas flow tube, pressure gauge,
and gas inlet and exit control valves. The bottle was
jacketed with a steel mesh sleeve and the entire set-up was
submerged in a mineral oil temperature bath. After charging
the reactor with catalyst and substrate the system was
purged of the ambient atmosphere by fi11ing-evacúating five
times with 1:1 H^rCO. The gases and CO were then
added to the desired pressure followed by heating of the oil
bath to the desired temperature.
Synthesis
Synthesis of silica bound propylaminosilane
The propylamine functionalized silica gel was prepared
10 8
using a method similar to that reported by Howell et al.
In a 500 ml round bottom flask equipped with a reflux
condenser, 150 ml of xylenes was added to 10 g of silica gel
(dried at 100°C under vacuum for 24 hours). While
stirring, the flask was purged with and then 11.07 g

15 5
(11.6 ml) of triethoxypropylaminos i1ane was added. The
mixture was then heated to reflux for 24 hours. After
cooling, the mixture was filtered, washed with xylenes, and
dried under vacuum at room temperature for 24 hours.
Analysis: C, 6.42%; H, 1.5%;'
N, 2.08%. Theoretical: C, 6.5%; H, 1.5%; N, 2.4%.
OH
HO
To a solution containing 0.5 g (0.00373 mole)
1,4-dihydroxy1-2,5-dibenzaldehyde in 200 ml absolute
ethanol, 1 g of propyl aminos i1ane bound silica gel
(synthesized by method 2) was slowly added. After 2 hours
of stirring the resulting orange resin was filtered, washed
extensively with absolute ethanol (1 liter) until no color
was observed in the filtrate, and dried under vacuum for 24
hours at 25°C. Analysis: C, 12.40%; H, 1.53%; N, 1.78%.
In a 125 ml Erlenmeyer flask equipped with a reflux
condenser 0.75 g of histamine • 2HC1 and 0.75 g sodium
bicarbonate were added to 30 ml absolute ethanol. While

156
stirring, the mixture was refluxed for 30 minutes. After
cooling, the solution was filtered, the solid washed with 50
ml of absolute ethanol, and the filtrate and washings were
combined. The resulting free base histamine solution was
added to a 300 ml round bottom flask containing 0.9 g of the
silica gel bound benzaldehyde in 150 ml of absolute
ethanol. The mixture was stirred under for 2 hours,
filtered and washed with absolute ethanol extensively. The
resulting orange resin was dried under vacuum for 14 hours
at 25°C. Analysis: C, 11.17%; H, 1.60%; N, 2.21%.
The synthesis of this Schiff base complex was derived
from a method reported by Folkers et al.^0^ In a 125 ml
Erlenmeyer flask equipped with a reflux condenser, 1 g
( 0.0054 mole) histamine-2HC1, 3 ml absolute ethanol and 1 g
sodium bicarbonate were mixed. While stirring, the mixture
was refluxed for 30 minutes. After cooling, the solution
was filtered, the solid washed with 50 ml absolute ethanol,

157
and the filtrate and washings combined. Under a
atmosphere 0.250 g (0.0037 mole) 1,4-dihydroxyl-2,5 -
d ibenzaldehyde was added to the histamine solution, and an
orange precipitate immediately formed. After stirring for
3 hours, the mixture was filtered and the precipitate was
washed with ethanol and dried under vacuum at 25°C for 30
minutes.
Rh(acac)(C0)2
Dicarbonyl(pentane-2,4-dionato)rhodium(I) was
synthesized by a procedure reported by Wilkinson and
109
Bonati. In a 100 ml round bottom flask equipped with a
reflux condenser 0.5 g of [RhCl(CO ) 7 ] ? , 1.668 g BaCO^,
and 1.25 ml acetylacetone were added to 42 ml of hexanes.
The mixture was refluxed with stirring for 1 week, cooled
and filtered to remove the BaCO^ precipitate. The volume
of solvent was reduced to 3 ml under vacuum. The reddish
green crystals were filtered, washed with a minimum amount
of hexanes and dried under vacuum for 10 minutes at 25°C.
Yield: 0.57g.
Rh(acac)(COD)
Cyclo-octa-l,5-diene(pentane-2,4-dionato)rhodiurn(I) was
synthesized by a procedure reported by Wilkinson and
109
Bonati. In a 100 ml round bottom flask 0.2 g
Rh(CO)2(acac) and 4 ml cyclo-octa-1,5-di ene was dissolved

158
in 20 ml (20-40°C) petroleum ether. The mixture was
stirred for 30 minutes at room temperature, the solvent
removed by vacuum, and the solid extracted with (40-60°C)
petroleum ether. After concentration of the solution, the
yellow solid which crystallized was filtered and air dried.
[Rh(Im)(COD)]x functionalized silica gel
In a round bottom flask 0.62 g histamine substituted
silica gel and 0.76 g Rh(acac)(COD) was added to 25 ml of
acetone. The mixture was stirred for 4 hours under N^.
The volume was reduced to 12 ml and the orange support was
filtered, washed with methanol and dried under vacuum for
24 hours at 25°C.
Results and Discussion
Synthesis - Imidazole Support
The synthetic route for the preparation of the 4(5)
substituted imidazole functionalized support is shown in
Figure 4-1. The method shown avoids the difficulties that
have been encountered when synthesizing a 4(5) substituted
imidazole silane. This is done by linking two readily
available reagents, the silane triethoxypropylam i nos i1ane
and the 4(5) substituted imidazole histamine using hydroxy
substituted dibenzaldehyde as the linking agent.

Figure 4-1. Synthetic route for the preparation of 4(5)
substituted imidazole functionalized
silica gel.

160
N
excess

161
Infrared spectroscopy proved to be an excellent probe
for following the sequence of reactions. Figure 4-2 shows
the IR spectra of intermediates in the region 1800-1400 cm
at various stages in the synthesis.
The first step in the synthesis involves a
condensation reaction of triethoxypropyláminos i 1ane, with
the silanol groups on the surface of the silica gel
generating the amino functionalized support I. Support I
was then contacted with an ethanol solution containing
I,4-dihydroxy1-2,5-dibenzaldehyde in a seven fold excess
(based on the theoretical concentration of amine groups
present) yielding the Schiff base functionalized support
II. Utilizing an excess of the dibenzaldehyde hopefully
minimized any cross linking of the type shown below.
The infrared spectrum of II (Figure 4 - 2 b) shows two
characteristic bands at 1629 cm ^ and 1670 cm ^ which
are assigned to the carbon nitrogen stretching mode of the
imine group (-N=C-) and the carbonyl stretching mode of
the aldehyde group respectively. The peak at 1670 cm ^
corresponds well with the carbonyl peak observed for the
infrared spectrum of 1,4-dihydroxy-2,5-dibenzaldehyde

Figure 4-2. Infrared spectra in the range 1800-1400 cm'
of functionalized silica gel and molecular
analogs.

163
1800

164
(Table 4-1). The presence of both an imine and an aldehyde
carbonyl band provide evidence for the proposed structure
of II and that one aldehyde group is still available on the
benzene ring for further reaction.
The reaction of free base histamine in a nine fold
excess with a solution of the benzaldehyde support II
resulted in the isolation of support III. This final step
in the synthesis is based on a Schiff base reaction shown
in Equation 3 reported by Heyl et al.^6 jn
reaction, pyridoxal was reacted with histamine in an
alcohol solution generating a stable imine linked
compound.
The infrared spectrum of III (Figure 4-2C) contains
only the band at 1626 cm ^ assigned to the stretching
frequency of the imine groups. The absence of the carbonyl
stretch of the aldehyde group observed for II indicates

165
Table 4-1. Infrared Stretching Frequencies Observed in
the Range 1800-1500 cm--*-.
a
Compound
y(C = 0) V ( C = N)
1626
1670 1629
1673
1631
a
Nuj ol mulIs.

166
that the remaining benzaldehyde groups of II successfully
reacted with histamine forming the second imine link.
The model compound shown below was synthesized and its
infrared spectrum shown in Figure 4-2d.
The single band observed at 1631 cm ^ corresponds well
with the imine stretching band observed for the imidazole
functionalized support III (Table 4-1).
An important consideration in synthesizing the
imidazole support III was the degree of surface coverage of
the imidazole groups that would be needed in order to allow
formation of the rhodium imidazolate trimer as shown below.

167
10 7
Based on an infrared study, Drago and Nyberg reported
that the concentration of organosulfide needed on the
surface of silica gel for the formation of predominantly
rhodium carbonyl dimer species shown below was 0.20 mmole
S per gram of silica gel. Based on the N analysis of III
(%N = 2.21%) theoretically 0.395 mmoles of substituted
imidazole per gram of silica gel is present. This
concentration should be more than sufficient to allow
trimer formation.
Hydroformylation
Metalation of the imidazole polymer was attempted by
the method^5 shown below (Equation 4) which was derived
from a reported synthesis of [Rh(RIm)(COD)]x (R=CH,, H
and refers to the 2 position of the imidazole ring)
complexes.
Rh(COD)(acac) + III > [Rh(Im)(COD)] (4)
Only preliminary results were obtained on the
hydroformylation activity of the functionalized rhodium

168
imidazolate catalyst. This system was tested for the
hydroformy1 ation of 1-hexene. The pressure reactor
described in the experimental section was charged with
0.25 g of the rhodium catalyst, 0.77 g of the promoter
PPh^, 10 ml 1-hexene and 80 psig with 1:1 H^CO. At
25°C no reaction was observed. On heating to 75°C a
pressure drop was observed at a rate of 80 psi/hr which
continued upon repeated pressurization to 80 psig with 1:1
Hz:C0.
During the course of the reaction, an aliquot of the
liquid was syringed from the reactor and analyzed by gas
chromotography. Two predominant products being formed were
n-heptanal and 2-methylhexanal. Assuming equal GC
sensitivity of the two products the ratio of normal to
branched was 3.9:1.
The degree of leaching of the catalyst into solution,
which is often a problem with immobilized catalysts, was
tested by filtering off the support and recharging the
filtrate with 80 psi of H^iCO gas. The filtrate was much
less active, a 60 psi pressure drop was observed after 48
hours. Recharging the filtered support also showed
diminished activity. Due to these preliminary results the
supported rhodium imidazole catalyst appears to be a very
active hydroformylation catalyst for 1-hexene but there
appears to be a fair amount of catalyst leaching taking
place.

169
One possible solution to the apparent leaching problem
is to utilize the catalyst in a fixed bed reactor (similar
to the system used in chapter 3) for the hydroformy1 ation
of a more volatile alkene such as 1-butene. A preliminary
test was performed but problems were encountered due to
plugging of the reactor caused by melting of the P(Ph)~
at reaction temperature. These results were inconclusive.
Conclusion
The objective of this study was to develop an
imidazole functionalized support that could be used to
heterogenize a homogeneous hydroformylation catalyst.
A convenient method for the synthesis of a 4(5)
substituted imidazole functionalized silica gel was
developed. To this authors knowledge, this is the first
successful synthesis of an imidazole functionalized support
in which the imidazole ring is attached through the 4(5)
position. Previous reports have shown the imidazole ring
attached through one of the ring nitrogens. Back
substitution on the imidazole ring frees both nitrogens
allowing the imidazole to act as a bridging ligand.
The synthetic method involved linking the 4(5)
aminoethyl substituted imidazole histamine to an
aminosilane functionalized silica gel by way of Schiff base
reactions with 1,4-dihydroxy-2,5-dibenzaldehyde. Infrared

170
spectroscopy proved to be an extremely useful tool for
following the course of the synthesis. The length and
flexibility of the organic chain connecting the imidazole
ring to the supported silane, along with a sufficient
coverage of the groups on the silica gel surface, should
allow the imidazole groups to obtain the desired
orientation for generating [Rh(Im)(COD) ] on the surface.
Preliminary results after metalation of the resultant
imidazole support with Rh(acac)(COD) showed this support,
in conjunction with a triphenylphosphine promoter, to be an
active catalyst for the hydroformylation of 1-hexene.
Problems with leaching of the metal catalyst into solution
were encountered using a slurry bed type system. An
attempt at using this catalyst in a fixed bed type reactor
for the hydroformylation of 1-butene was inconclusive due
to experimental difficulties.
The synthesis and potential use of a 4(5) substituted
imidazole support to attach homogeneous catalysts has been
demonstrated. Further work in the future should be
undertaken to illustrate the full potential of this
hydroformylation catalyst. Other uses of this type of
imidazole support need to be explored. These include the
potential use in other catalytic systems or possibly in the
modeling of metaloenzymes like carbonic anhydrase.

V. SOLUBLE BIMETALLIC COMPLEXES
Introduction
In Chapter Three of this thesis, synergistic
interactions between two separate metal centers aiding the
reduction of carbon monoxide by hydrogen were illustrated.
The synthesis and characterization of macromolecules capable
of binding two metal centers in close proximity within the
same molecule is a natural extension of this work. The
synergistic interactions between metal centers in the same
molecule not only has relevance to the area of catalysis but
also to metallobiomolecules and electron transfer processes.
Many metaloenzymes contain multimetal centers. Hemocyanin,
lacease and tyrosinase'*’*'^’ * * ^ contain coupled binuclear
117
copper sites and superoxide dismutase may involve a
Cu-Zn active center.
A large number of complexes have been synthesized
utilizing ligands capable of binding two metals in close
proximity that lack solubility in all but strong donor
118-17? 1?"^
solvents. Recently, Drago et al. have
reported a series of bimetallic complexes based on the
ligand shown below which are soluble in non-polar solvents
such as CH^Cl. This prevented the system from being
limited to only solid state measurements or solution studies
in donor solvents.
171

172
In this study a number of bimetallic complexes having
the proposed structure shown below have been synthesized
and characterized, and have the potential for the
activation of small molecules such as , CO, C^H^,
etc. These complexes are based on the ligand
M = Cu, Zn,
BE,
[M(DIOX)BF2]2
Ni,
Pd
bi s-4 - tert-buty1-2,6-diformy1-pheno1 dioxime, derived from a
12 3
precursor of the ligand reported by Drago et al. When
reacted with BF^ • Et^O these complexes demonstrate
solubility in poor donor solvents such as acetone.

173
Experimenta 1
Materials
All reagents and solvents were used as purchased unless
otherwise stated. The reagent 4 - tert-buty1-6-formy1sa1 icy1-
aldehyde was supplied by Mike Desmond and was synthesized by
12 3
the procedure reported by Drago et al. Acetone used
was dried by a literature reported method.^^ Reagent
grade acetone was saturated with dry Nal and frozen at
-15°C. The unfrozen liquid was decanted and the frozen
solid distilled. N,N-Dimethylformamide (DMF) was refluxed
over BaO for 48 hours, then distilled under nitrogen.
Instrumentation
Elemental analyses were performed by the
Microanalytical Laboratory, University of Florida,
Gainesville, Florida. Infrared spectra were recorded as
Nujol mulls on a Perkin Elmer 283B spectrometer.
Cyclic voltammetry was carried out in DMF and acetone
electrolyte solutions. All voltammograms were recorded by
sweeping from the most positive potential to the most
negative and back (100 mV/s). Cyclic voltammetry was
conducted using a PARC model 175 Universal Programmer and a
PAR 173 Potentiostat/Galvanostat.

174
Voltammograms were recorded on a Houston Instrument X-Y
Omnigraphic 2000 Recorder.
The electrochemical cell used was a modified version of
12 5
a cell reported by Desmond (Figure 5-1) and consisted
of a three electrode arrangement. The auxiliary electrode
was a course grade frit with a coiled Pt wire inside. The
working electrode (constant area) was made by sealing a Pt
wire in the end of a glass tube. There were two types of
reference electrodes used in this study. Ag/AgI was used
when acetone was the solvent. The electrode was made by
attaching a "Vycor" tip to the end of the glass tube. The
tube was then filled with equal amounts of 0.05M Bu^NI and
0.1M Bu^NClO^. The added solution was then saturated
with Agl and a Ag wire was inserted down the tube just
lightly making contact with the tip. The electrode was
allowed to equilibrate in a storage container that was also
filled with equal amounts of 0.05M Bu4NI and 0.1M
Bu-,NC10^ for one week. A Ag/AgCl electrode was used
when DMF was the solvent and was made as described by
12 3
Drago et al. The electrolyte solutions used in these
experiments were 0.10M Bu^NClO^ in acetone and 0.1M
Bu.NClO. in DMF.
4 4
The reduction potentials reported were referenced to
the ferrocene/ferrocinium couple. The ferrocene/ferrocinium
couple occurs at 0.160 V relative to aqueous SCE and 0.40 V
12 6
relative to NHE and are assumed to occur at the same
12 7
redox potential in both solvents.

Figure 5-1. Cyclic voltammetry cell.
A. Reference electrode with "VYCOR" tip (Ag/AgCl and
Ag/AgI).
B. Counter electrode, platinum wire coil enclosed in coarse
grade frit.
C. Working electrode with platinum button at the tip.
D. E, F. Openings for reference, counter, and working
electrodes.
G. Gas outlet attached to bubbler.
H, I. Teflon valves.
J. 50/50 ground glass male joint.
K. 50/50 ground glass female joint.

176

Synthes is
(DIOX)
177
Bis-4-tert-butyl-2,6-diformyl-phenol dioxime, was
prepared by a method patterned after a procedure reported by
12 8
Baucom and Drago. In a 250 ml round bottom flask
equipped with a reflux condenser, 6.30 g of freshly
recrystallized 4-tert-butyl-6-formylsalicylaldehyde from
hexanes was combined with 2.6 g NaOH, 4.5 g NH^OH • HC1 and
30 ml 50% aqueous methanol. The 4-tert-butyl-6-formyl-
salicylaldehyde was synthesized by and obtained from M.J.
12 5
Desmond. The mixture was heated while stirring on a
steam bath for 1.5 hours. After cooling, the brown
precipitate was filtered and washed with H^O. The light
brown solid was then dried under vacuum for 4 hours at
5 0°C. Analysis: C, 61.31%; H, 6.86; N, 11.68%.
Theoretical: C, 61.0%; H, 6.8%; N, 11.9%.
[Cu(DI0X)0H0]2
In a 100 ml beaker, 0.755 g DIOX (3.07 mmole) was
combined with 0.748 g Cu(N0^)2* 3H20 (3.07 mmole) and
60 ml MeOH. The solution was heated while stirring and was
maintained at reflux temperature for 15 minutes. After
cooling, the dark green precipitate was filtered, washed
with methanol and dried under vacuum for 24 hours at
6 0°C. Analysis: C, 48.14%; H, 4.71%; N, 9.13%.
Theoretical: C, 48.4%; H, 4.8%; N. 9.4%.

178
[Zn(DIOX)OHO ] 2
In a 50 ml beaker, 0.5 g DIOX (2.03 mmole) was combined
with 0.446 g Zn(acetate)^* H^O (2.03 mmole) and 30 ml of
methanol. Immediately, a white-ish precipitate formed. The
mixture was heated while stirring and maintained at reflux
temperature for 15 minutes. After cooling the solid was
filtered, washed with methanol and dried under vacuum over
P-,0,- for 6 hours at 2 5 °C. Analysis: C, 47.46%; H, 4.89%;
N, 8.98%. Theoretical: C, 48.09%; H, 4.72%; N, 9.35%.
[Pd(DI0X)0H0]2
In a 50 ml beaker, 0.24 g DIOX (0.974 mmole) was
combined with 0.228 g Pd(N0^)2* H^O and 30 ml
methanol. The mixture was heated while stirring and
maintained at reflux temperature for 15 minutes. After
cooling, the brown precipitate was filtered, washed with
methanol and dried under vacuum at 60°C for 4 hours.
Analysis: C, 43.39%; H, 4.42%; N, 8.73%. Theoretical:
C, 42.30%; H, 4.15%; N, 8.22%.
[ N i (DIOX)OHO ]2
In a 50 ml beaker 0.5 g DIOX (2.03 mmole) was combined
with 0.50 5 g Ni(acetate)^* 4H^0 (2.03 mmole) and 30 ml
methanol. Immediately, a green precipitate formed. On
heating and stirring the precipitate turned light brown.
After stirring at reflux temperature for 15 minutes the

179
mixture was cooled, filtered and washed with methanol. On
drying under vacuum over P^O,- at 25°C for 6 hours, the
light brown solid turned green. Analysis: C, 48.20%;
H, 4.77%; N, 8.85%. Theoretical: C, 49.2%; H, 4.85;
N, 9.56%.
[Cu(DI0X)BF2]2 • 2H20
The method used for this synthesis was patterned after
12 9
the procedure reported by Schrauzer and Windgassen. In
a 50 ml round bottom flask, 0.459 g [Cu(DI0X)0H0(0.77
mmole), 1.10 ml BF-j-Et^O (9.69 mmole) and 12 ml Et?0
were combined. The mixture was stirred for 20 hours at
Q
25 C under nitrogen. The solvent and excess BF^ Et^O
were removed under vacuum and the resulting dull green solid
was further dried under vacuum at 25°C for 2 hours. The
solid was recrystallized in a minimum amount of CH^CN.
The resulting microcrystalline product was dried under
vacuum at 60°C. Analysis: C, 39.55%; H, 4.05%; N, 7.62%.
Theoretical: C, 39.63%; H, 4.17%; N. 7.71%.
[Zn(DI0X)BF2]2 MeOH
In a 50 ml round bottom flask 0.5 g [Zn(DI0X)0H0 ] 2 ,
2 ml BF^'Et^O and 10.0 ml Et20 were combined. After
stirring for 24 hours at 25°C under nitrogen, the white
solid was filtered and washed well with Et^O. The solid
was vacuum dried for 4 hours at 25°C. Recrystallization

180
in a minimum amount of methanol and drying under vacuum at
25°C yielded a white crystalline solid. Analysis:
C, 41.66% ; H, 4.395 ; N, 7.75% Theoretical: C, 41.30%;
H, 4.16%; N, 7.70%.
[Pd(DI0X)BF2]2
In a 50 ml round bottom flask, 0.21 g [Pd(DIOX)OHO],
I.80 ml BF,»Et20 and 10.0 ml Et-,0 were combined.
After stirring for 20 hours at 25°C under nitrogen, the
brownish red precipitate was filtered, washed with Et^O
and dried under vacuum at 25°C. Analysis: C, 38.38%; H,
4.00%; N, 6.95%. Theoretical: C, 37.10%; H, 3.38%; N,
7.21%.
[Ni(DIOX)BF2]2 7H20
In a 50 ml round bottom flask, 0.18 g
[Ni(DIOX)BFo]2> 1.5 ml BF,»Et20 and 10.0 Et20 were
combined. After 24 hours of stirring at 25°C under
nitrogen, the greenish precipitate was washed with Et20.
Upon air drying, the solid turned purplish white. Drying
under vacuum at 68°C for 15 minutes caused the color of
the complex to return to its original green color. The
purplish white solid was analyzed. Analysis: C, 35.75%;
H, 4.62%; N, 6.79%.
N, 6.93%.
Theoretical: C, 35.69%; H, 5.0%;

181
[Ni(DIOX)OH2]2Cno3J 2 * 2H2°
In a 100 ml beaker, 0.5 g DIOX (1.03 mmoles) was
combined with 0.446 g Ni(NO^)-, • 6H?0 (2.03 mmole) and
60 ml methanol. The mixture was heated while stirring and
maintained at reflux temperature until the volume was
reduced to 30 ml. After cooling, addition of diethyl ether
yielded a grey blue precipitate. The solid was filtered and
dried under vacuum. Analysis: C, 38.60%; H, 4.55%; N,
11.10%. Theoretical: C, 38.5%; H, 4.6%; N, 11.2%.
Results and Discussion
Ligand Preparation
The synthetic route for the preparation of bis-4-tert-
butyl-2,6-diformy1-phenol dioxime, DIOX, is shown below
(Equation 1) and is based on a procedure reported by Baucom
12 8
and Drago. Successful synthesis of DIOX was confirmed
(1)

182
by elemental analysis, which showed excellent agreement
between the predicted theoretical and experimental values
for the percentage C, H, and N (Table 5-1).
The most difficult part of synthesizing the DIOX
ligand was obtaining the diaTdehyde reagent,
4-tert-buty1 -6-formy1 salicylaldehyde. Its synthesis
entails a fairly lengthy procedure developed by Desmond
123 125
et al., ’ whom graciously supplied the reagent for
use during this study.
Metalomers, Synthesis and Characterization
Combining an equimolar amount of DIOX ligand with the
acetate or nitrate salt of any of the divalent cations Cu,
Zn, Pd, or Ni results in the formation of a bimetallic
complex which is believed to have the structure shown below.
[m(diox)oho]2

Table 5-1. Elemental Analysis of the DIOX Ligand and Metal DIOX Complexes.
Complex
C
Caled. %
H
N
C
Found %
H
N
DIOX
61.0
6.8
11.9
61 .31
6.86
11.68
[Cu(DIOX)OHO]2
48.4
4 . 8
9.4
48. 14
4 .71
9. 13
[Zn(DIOX)OHO]2
48. 1
4 . 7
9.4
47.46
4 . 89
8. 98
[Pd(DIOX)OHO]2
42.3
4.2
8.2
43.39
4 .42
8. 73
[Ni(DIOX)OHO]2
49.2
4.8
9. 6
48.20
4 . 77
8. 85
[Ni(DI0X)(0H)2]2 C N03)2 * 2H2 0
38.5
4.6
11.2
38.60
4.35
11.10
[Cu(DIOX)BF2]2 • 2H2 0
39.6
4.2
7. 7
39. 55
4.05
7. 62
[Zn(DI0X)BF2]2 . MeOH
41.3
4.2
7. 7
41.66
4.39
7. 75
[Pd(DIOX)BF2]2
37. 1
3.4
7.2
38.38
4.00
6. 95
[Ni(DIOX)BF2]2 • 7H2 0
35.7
5.0
6. 9
35.75
4 . 62
6. 79
183

184
The structure consists of two divalent cations bridged by
two phenoxy groups and further bound through the nitrogens
of the four oxime groups. Infrared analysis supports the
existence of the capping 0-H***0 groups on each side of the
molecule. A representative i'nfrared spectrum for these
complexes is shown in Figure 5-2 for the copper system.
In all four complexes a broad band around 1750 cm 1
was observed due to the presence of 0-H***0 bridging
groups. These bands are in a range similar to that reported
for the complex CH,Co(DH) ,Py shown below (v'q^q = 1740 cm ).
O
l
• N
H
Co
N CH3 N
o o
•H
CH3Co(DH)?Py
Table 5-2 lists the 0-H*-*0 group frequencies observed for
the various metal complexes along with the frequencies of
the bands assigned to C=N stretches, which also occur in a
range similar to complexes previously reported.1"'9,15^
Elemental analysis of the complexes shown in Table 5-1
also agree with the proposed structure. Thus these
complexes of the formula [M(DI OX)OHO]2 are neutral with
each DIOX ligand effectively having a formal negative two
charge.

Figure 5-2. Infrared spectrum of [Cu(DIOX)OHO, Nujol mull.
185

Table 5-2. Infrared Bands Observed in the Frequency Range 1800-1500 cm-1.
Compound
V CO-H •
• • 0 ) cm
y(C = N) cm'1
[Cu(DIOX)OHO]2
1742
(Br)
1561
[Zn(DIOX)OHO ]2
1723
(Br)
1557
[Ni(DIOX)OHO ]2
1758
(Br)
1552
[Pd(DIOX)OHO]2
1770
(vBr)
1550
[Ni(DIOX)(OH)2]2(NO3)2 • 2H2 0
1553
CH3 Co(DH)Pya
1740
(Br)
1548
ClCo(DH)Pyb
1710
a Schrauzer and Windgassen 1 ^9 DII = d ime thylg lyox ime anion.
b Gillard and Wi lkinson.
186

187
The metal salt used, either the acetate or nitrate, was
found to have an affect on the bimetal complex produced in
the nickel system. When NiCacetate)^ was used as the
nickel source the usual 0-H***0 bridged complex was formed.
If NiiNO^)^ was used a cationic non 0-H • • •0 bridged
complex was formed and is believed to have the structure
shown below.
M = Ni
[NiCDIOX)(OH)2 ]2
This complex can be isolated as a nitrate salt by addition
of ether to the reaction mixture. Infrared spectra of the
products formed from Ni(acetate)2 and Ni(NO^)2 are
shown in Figures 5-3 and 5-4 respectively. It can be
quickly seen that the spectrum of the complex formed from
NiCNOj)^ does not contain the broad 0-H***0 band at
1758 cm-^ and contains bands above 3000 cm ^ due to

100
3500
3000
2500
2000 1800
Wavenumber
Figure 5-5. Infrared spectrum of [Ni(DIOX)OHO]7
.i—1__—.—.—i—.—i—.—i—.—.—.—i—.—.—.—i—.
1600_ 1400 1200 100-0 800
cm'1
Nujol mull.
188

Figure 5-4. Infrared spectrum of [Ni(DI OX)(OH^ (^03)2> ^ujol mull.
189

190
0-H stretches of the oxime groups. Elemental analysis
(Table 5-1) also agrees well with the above proposed
structure. This behavior was not observed in the Cu
system. Regardless of the Cu source, nitrate or acetate,
the same 0-H***0 bridged complex was formed. Thus it
appears that in the nickel case a stronger base such as
acetate is needed to abstract a proton from one of the oxime
0-H groups to allow formation of a 0-H»**0 cap.
The 0-H*»*0 bridged complexes showed very poor
solubilities in non polar solvents and only slight
solubility in polar solvents such as DMSO and hot
acetonitrile. In an attempt to improve the solubility the
complexes were reacted with BF^-Et^O forming the BF 0
capped complexes as shown in Equation 2. This reaction was

191
patterned after work reported by Schrauzer and
129
Windgassen.
Elemental analysis of the four metal complexes (Cu, Ni
Pd, Zn) indicated successful conversion of the 0-H**»0
bridge to a BF^ cap. Infrared spectra of the resulting
complexes lacked the 0-H***0 band usually observed at about
1 750 cm . A representative infrared spectrum for these
complexes is shown in Figure 5-5 for the copper system. In
addition a large, very broad absorbance at about 1050 cm 1
was observed which is difficult to assign but probably can
be attributed to the bridging BF^ groups. (B-F stretches
have been found to occur in the range 750-1500 cm ^) .
The nickel BF^ bridged complex demonstrates some
interesting chemistry not observed for the other metal
complexes. The infrared spectrum of the green, vacuum dried
complex (68°C, 1.5 hours) is shown in Figure 5-6. On
exposure to air the complex quickly turned to a
purplish-white color, and its infrared spectrum is shown in
Figure 5-7. The only major difference in the two spectra
was in the 3000-4000 cm ^ region which indicates the color
change was due to adsorbed H90. The complex can be
reversibly returned to the green color upon vacuum drying.
Elemental analysis indicated the presence of about seven
1U0 per complex.
The four BF^ capped complexes, unlike the 0-H»**0
bridged complexes, were soluble in acetone, methanol,
ethanol, CH^CN and DMF. These complexes were insoluble in

100
• 21^0, Nujol mull.
Figure 5-5. Infrared spectrum of [Cu(DIOX)BF^]¿
192

Figure 5-6. Infrared spectrum of [ Ni (DI0X)BF2 ] ? • xll2 0 , Nujol mull.
193

Figure 5-7. Infrared spectrum of [Ni(DIOX)BF,• 7H¿0, Nujol mull.
194

195
toluene, Et^O and H^O. Recrystallization of [Cu(DI OX)BF^]^
by slow evaporation of a methanol solution yielded crystals
that could be used for an X-ray structure analysis.
Electrochemistry
The reduction potentials of [Cu(DI OX)BF^]2 relative
to ferrocene/ferrocinium couple were obtained in two solvent
systems, acetone and DMF and are shown in Table 5-3. Cyclic
voltammograms showed two redox couples in both acetone and
DMF, and the voltammogram obtained in DMF is shown in Figure
5-8. Based on the fact that the difference between the peak
potentials is greater than 60 mV, the theoretical value for
a one electron transfer, the two redox couples appear to be
quasireversib 1e one electron transfers.^^ These redox
couples are assumed to represent the stepwise reduction of
the two Cu(II)'s to CU(I)'s then stepwise reoxidation back
to Cu(11)'s.
The differences between redox couples, can be
119 132
used to estimate K , ’ the equilibrium constant
con ’ n
for the conproportionation reaction below. The value of the
^con indicates the stability of the Cu( I) Cu( 11) L" mixed
^con
Cu(I)Cu(I)L2- + Cu(II )Cu(II)L ~—* 2.Cu(I)Cu(11)L- (3)
Ex -E 2 = . 0591 log Kcon (4)
valence state. If two metal centers are totally

Table 5-3. Electrochemistry of Cu2 Complexes.3
Complex
Solvent
1 b
El/2 ,V
V, mV
2 b
El/2 >V
V, mV
El-E2
[Cu(DI0X)BF2]2 • 2H2 0
Acetone
-0. 86
90
-1.34
73
.48
DMF
-0.93
91
-1.40
156
.47
Cu2BB(0Et)C
CH2C12
-1.06
222
-1.78
235
. 72
DMF
-1.10
151
-1 . 60
270
. 50
d
[Cu2 L][Cl04 ] 2 * 2H2 0
DMF
e
- . 917
3 Cyclic voltammetry under N2 atmosphere, scan rate 100 mV/s. b Potentials
relative to an internal standard, ferrocene/ferrocinium couple. c Drago et al.,^3
d Gagne et al.,9 L = N and 0 donor macrocyclic ligand, obtained from polarography.
196

Cyclic voltammogram of [Cu(DIOX)BF232 in
DMF electrolyte at a scan rate of 100mV/s
under N2 (referenced to ferrocene/ferrocinium
couple) .
Figure 5 - 8.

¡Cu[diox1bf2]2
in
DMF
, i . . i , . -—i—. . . i —.—i
"1.64 "1.84 "2.04 “2.24
198

199
non-interacting, K =4. Values of K greater than
1 x 10^ have been found to be Class II and values greater
than 1 x 10^0, Class III (the electron completely
delocalized) mixed valence complexes.
The values of K calculated for acetone and DMF are
con
8 9
1.3 x 10 and 1.1 x 10 , respectively. These results
indicate that the [ Cu( 11) Cu( I) (DIOX) BF ,, ] might be
12 3
approaching Class III. The Kcon values reported for
Cu(II)Cu(I)BB(OEt) in both a non-coordinating and
coordinating solvent, CH^Cl^ and DMF, showed a large
solvent dependence resulting in Kcon values equal to
8 12
3 X 10 and 2 x 10 . The solvent dependence observed
in the Cu^DIOX system was much smaller than for Cu^BBÍOEt)
for reasons that are not fully understood but may result
from the absence of a removable anionic bridge (OEt )
which is present in Cu^BBiOEt).
Electrochemical studies of [ Zn( DIOX^F^ ] ^ showed no
redox activity in the range allowed by the solvent and
electrolyte. The corresponding Ni and Pd complexes were
not well behaved and showed complicated irreversible redox
couples.
Conclusion
In this study a series of bimetallic complexes of the
formula [M((II)(DI0X)OHO]^, where M=Cu,Ni,Zn or Pd, have

200
been synthesized using the ligand b i s-4 - tert-buty1-2,6 -
d i foriny 1 -pheno 1 dioxime. The insoluble 0-H**»0 bridged
complexes on reaction with BF^*Et,0 are transformed into
BF-, capped complexes which are soluble in poor donor
solvents such as acetone. This solubility allows solution
studies to be carried out. In the past, solution studies of
reported bimetallic ligands has proven difficult due to
their lack of solubility in all but strong donor solvents.
Preliminary electrochemical studies were performed on
the Cu(II) dimer which demonstrated a strong interaction
between the two Cu(II) centers. Further work is needed to
pursue the chemical and the potential catalytic properties
of these complexes.

VI. SUMMARY AND CONCLUSION
The results obtained from the four studies presented
here provided a fundamental understanding and insight into
future catalytic processes which involve the activation of
carbon monoxide and/or hydrogen. In the first study
enthalpies of hydrogen activation were obtained for a
typical hydrogenation catalyst and its derivatives. The
enthalpies obtained were found to be independent of the
variations made in the ligand environment about the rhodium
metal center.
The second study investigated immobilized homogeneous
CO reduction catalysts as selective catalysts for producing
chemicals from syngas. Ionic attachment of two ruthenium
anions to an ammonium iodide functionalized silica gel was
demonstrated but showed no syngas conversion activity. A
covalently attached Ir^(CO)^ cluster in combination
with a Lewis acid co-catalyst was found to show excellent
selectively for the conversion of syngas and HC1 to CH^Cl
under very mild conditions.
In the third study a new type of catalyst support was
synthesized which was designed for potential use in
supporting a known homogeneous rhodium imidazole
hydroformylation catalyst. This study demonstrated the
201

202
first successful synthesis of a 4(5) substituted imidazole
functionalized silica gel.
In the fourth and final study a series of soluble
bimetallic complexes were synthesized and characterized
which have potential for use as bifunctional catalysts.
Electrochemical studies illustrated strong metal site
interactions.

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BIOGRAPHICAL SKETCH
The author was born on September 11, 1957, in Ithaca,
New York. He attended public schools in Ithaca and
graduated from Ithaca High School in June 1975. In August
1975, he entered Ithaca College, Ithaca, New York, from
which he graduated with a B.A. degree in chemistry in May
1979.
In August 1979, he entered the graduate school of the
University of Illinois at Urbana-Champaign and he began his
graduate work in inorganic chemistry. In June 1982, he
transferred to the graduate school at the University of
Florida, Gainesville, Florida (following his graduate
research advisor's transfer). He completed his graduate
work in inorganic chemistry in 1985. During his graduate
study, he held various teaching and research assistantships.
On June 20, 1981, he married the former Nancy M.
Holcomb in Ithaca, New York. On May 7, 1984, the author
began employment with Union Carbide Corporation, Tarrytown,
New York, as a Staff Chemist in the Catalyst and Process
Systems Division.
He is co-author of the following publications and
patent:
211

212
1. "Synthesis and Characterization of Copper (II)
Squarate Complexes," J.T. Reinprecht,
J.G. Miller, G.C. Vogel, M.S. Haddad,
D.N. Hendrickson, Inorg. Chem. (1980), 19,
927 .
2. "Copper (II) Incorporation into Tetraphenylporphine
in Dimethyl Sulfoxide," R.F. Pasternack,
G.C. Vogel, C.A. Skowronek, R.K. Harris,
J.G. Miller, Inorg. Chem. (1981), 20, 3763.
3. "An NMR and Calorimetric Investigation of the
Reaction of Square Planar Rhodium (I) Compounds
with H-,," R.S. Drago, J.G. Miller,
M.A. Hoselton, R.D. Farris, M.J. Desmond,
J. Am. Chem. Soc. (1983), 105, 444.
4. "Method for the Preparation of Halogen Substituted
Methanes and Ethanes," Patent Application
No. 603,301. R.S. Drago, J.G. Miller, K. Weiss.

I certify that I have read this study and that in my opinion
it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
kusselí S.
Professor
/
>(
Drag o
of Chemistry
I certify that I have read this study and that in my opinion
it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
HarryJj-rfS i s 1 e r
ngcrished Service Professor
Chemis try
I certify that I have read this study and that in my opinion
it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
Assistant Professor of Chemistry
I certify that I have read this study and that in my opinion
it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
Anna Brajte^r-Toth
Assistant Professor of Chemistry

I certify that I have read this study and that in my opinion
it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
l\jut —
Waldo R. Fisher, M. D .
Professor of Biochemistry and
Molecular Biology
This dissertation was submitted to the Graduate Faculty 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.
December, 1985
Dean, Graduate School

UNIVERSITY OF FLORIDA
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