A synthetic, structural and theoretical investigation of pentadentate Schiff base ligands

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Title:
A synthetic, structural and theoretical investigation of pentadentate Schiff base ligands
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xi, 145 leaves : ill. ; 29 cm.
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English
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Sommerer, Shaun O., 1962-
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Thesis:
Thesis (Ph. D.)--University of Florida, 1991.
Bibliography:
Includes bibliographical references (leaves 140-144).
Statement of Responsibility:
by Shaun O. Sommerer.
General Note:
Typescript.
General Note:
Vita.

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University of Florida
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All applicable rights reserved by the source institution and holding location.
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Full Text











A SYNTHETIC, STRUCTURAL AND THEORETICAL INVESTIGATION
OF PENTADENTATE SCHIFF BASE LIGANDS















By

SHAUN O. SOMMERER


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


1991






















ACKNOWLEDGMENTS

I wish to thank my research director Gus J. Palenik for

his help and guidance during the course of this project,

Gaines Martin and Tom Cundari for the helpful discussions

concerning the work presented in Chapter 5, and John David

Baker for his introduction, help and patients in ZINDO land.

There are a myriad of other people who have helped me in

the course of this project and in making my way through

graduate school. I thank all of you and leave you with this

wish (which I borrowed from B. Dylan)



.... may your heart always be joyful,

may your song always be sung,

and may you stay forever young.















TABLE OF CONTENTS


ACKNOWLEDGMENTS . . ii

LIST OF TABLES ............ iv

LIST OF FIGURES . . .. vi

ABSTRACT ................ .vii

CHAPTERS

1 INTRODUCTION. . .... .. 1

2 PENTAGONAL BIPYRAMIDAL COMPLEXES OF Sn(IV),
Ti(III), AND Cu(II) . 6
Introduction ....... 6
Experimental .......... 7
Results and Discussion . 27

3 A NOVEL PENTAGONAL BIPYRAMIDAL IRON
COMPOUND: UNCONNECTED Fe(II) AND Fe(III)
MOLECULES WITHIN THE SAME ASYMMETRIC UNIT 38
Introduction .......... 38
Experimental ............ .39
Results and Discussion .41

4 PENTAGONAL BIPYRAMIDAL COMPLEXES OF Cr(III)
WHICH DISPLAY A STATIC JAHN-TELLER
DISTORTION . .. 54
Introduction. . .. 54
Experimental .. .... 55
Results and Discussion .. .57

5 SYNTHESIS AND CRYSTAL STRUCTURE OF A WATER
SOLUBLE CATIONIC (n13, -CC1oH6)Ru(IV)
COMPLEX: CHLORO[(1-3-: 6-8- )-2,7-
DIMETHYLOCTADIENEDIYL]SEMICARBAZIDE
RUTHENIUM(IV) CHLORIDE DIHYDRATE 84
Introduction . 84
Experimental ........... .85
Results and Discussion. .92
Conclusion. . .. 100









6 A THEORETICAL INVESTIGATION OF THE
ELECTRONIC AND STRUCTURAL PROPERTIES
OF THE LIGAND DAPSC AND THE PENTAGONAL
BIPYRAMIDAL COMPLEX DIAQUO-
(2,6-DIACETYLPYRIDINEBIS(SEMICARBAZONE))
IRON(II) ...... ......... 101
Introduction . .. 101
Calculations . 104
Discussion . 115

APPENDIX . .. 127

REFERENCES . .. .. 140

BIOGRAPHICAL SKETCH . . 145











Table 2-1


Table

Table

Table

Table

Table

Table


Table

Table

Table

Table


2-2

2-3

2-4

2-5

2-6

2-7


2-8

2-9

2-1

2-1


Table 2-1;


Table 2-1


Table 3-1


Table 3-2


Table 3-3


Table 3-4


Table 3-5



Table 4-1


LIST OF TABLES

Crystal Data for Sn(DAPSC)Cl22,
Ti(DAPBAH)C12, and Cu(DAPAAH)Cl(H20)

Atomic Parameters for Sn(DAPSC)Cl2 .

Atomic Parameters for Ti(DAPBAH)C12 .

Atomic Parameters for Cu(DAPAAH)Cl(H20) .

Bond Distances and Angles for Sn(DAPSC)Cl2*

Bond Distances and Angles for Ti(DAPBAH)C1,

Bond Distances and Angles for
Cu(DAPAAH)Cl(H20) . .

Anisotropic U values for Sn(DAPSC)Cl22 .

Anisotropic U values for Ti(DAPBAH)C1, .

0 Anisotropic U values for Cu(DAPAAH)Cl(H20)

1 Hydrogen Atomic Parameters for
Sn(DAPSC)C 2 . .

2 Hydrogen Atomic Parameters for
Ti(DAPBAH)C12 . .

3 Hydrogen Atomic Parameters for
Cu(DAPAAH)Cl(H20) . .

Atomic Parameters for Fe(II)/(III)
(DAPSC)Cl(H0) . .

Bond Distances and Angles for Fe(II)/(III)
(DAPSC)C1(H20) . .

Anisotropic U values for Fe(II)/(III)
(DAPSC)C1(H20) . .

Hydrogen Atomic Parameters for Fe(II)/(III)
(DAPSC)C1(H20) . .

Bond Lengths Observed Within the Immediate
Coordination Sphere for Fe(II)/(III)
(DAPSC)Cl(H20) and related compounds

Crystal Data for Cr(DAPSC)(H20)2 and
Cr(DAPBAH)(H20), . .


10

11

12

13

14

15


17

18

20

22


24


25


26


44


46


48


50



52


58









Table

Table

Table


4-2

4-3

4-4


Table 4-5


Table

Table

Table


4-6

4-7

4-8


Table 4-9


Table 4-1



Table 5-1


Table 5-2


Table 5-3


Table 5-4


Table 5-5


Table

Table


5-6

6-1


Table 6-2


Atomic Parameters for Cr(DAPSC)(H0) .

Atomic Parameters for Cr(DAPBAH)(H0) .

Bond Distances and Angles for
Cr(DAPSC)(H20)2 . .

Bond Distances and Angles for
Cr(DAPBAH)(H20)2 . .

Anisotropic U values for Cr(DAPSC)(H20)2

Anisotropic U values for Cr(DAPBAH)(H20)2 .

Hydrogen Atomic Parameters for
Cr(DAPSC)(H20)2 .

Hydrogen Atomic Parameters for
Cr(DAPSC)(H )2 . .

) Bond Distances Within the Coordination
Sphere for Cr(DAPSC)(H0O)2 and
Cr(DAPBAH)(H20)2 . ..

Crystal Data for (1~3, I3-CoH16)Semicarbazide
Ru(IV) Chloride . .

Atomic Parameters for (T3, y13-CoH,6)
Semicarbazide Ru(IV) Chloride .

Bond Distances and Angles for (T13, ,3-CoH6)
Semicarbazide Ru(IV) Chloride .

Anisotropic U values for (t13, 13-CoH16)
Semicarbazide Ru(IV) Chloride .

Hydrogen Atomic Parameters for (i3, 3-CoH16)
Semicarbazide Ru(IV) Chloride .

Summary of the Ru-Cl Bond Distance .

Bond Distances and Angles for the
Geometrically Optimized DAPSC .

Bond Distances and Angles for the
Geometrically Optimized
Fe(DAPSC)(H0)22 . .


59

60


62


63

66

68


71


72



76


87


88


89


90


91

99


107



120









Table 6-3 A Summary of the Bond Distances Within the
Immediate Coordination Sphere for an
Fe2* Center in Singlet, Triplet and
Quintet Spin States. .. 121

Table 6-4 Relative Total Energies of the Three Optimized
Spin States . .. 122


vii











Figure 1-1


Figure

Figure

Figure


2-1

2-2

2-3


Figure 3-1


Figure 4-1


Figure 4-2


Figure 4-3


Figure 4-4


Figure 5-1


LIST OF FIGURES

Graphic Representation of the Ligands
DAPSC, DAPBAH and DAPAAH .

An ORTEP Representation of [Sn(DAPSC)C1,2

An ORTEP Representation of Ti(DAPBAH)Cl2

An ORTEP Representation of
[Cu(DAPAAH)Cl(H0)* .

An ORTEP Representation of an Fe(II/III)
DAPSC Complex . .

An ORTEP Representation of
[Cr(DAPSC)(H20)2 . .

An ORTEP Representation of
[Cr(DAPBAH)(H)20) 2+ ..

Crystal Field Splitting Diagram for a
Pentagonal Bipyramidal Field .

A Representation of the Half-Conjugated
Monoanion form of DAPSC .

An ORTEP Representation of (13,n13-Co1H16)
Semicarbazide Ru(IV) Chloride .


Figure 5-2 A Representation of the Bonding,
Non-bonding and Anti-bonding Molecular
Orbitals for a 3-electron T -allyl
function . .

Figure 6-1 Representations of the DAPSC Ligand in
Low Energy Conformations .

Figure 6-2 A Representation of DAPSC in the Optimum
Geometry as Determined by ZINDO .

Figure 6-3 An Illustration of the Relative Total
Energy vs. the Angle of Rotation for
DAPSC with One Semicarbazone "arm"
Locked Forward . .

Figure 6-4 An Illustration of the Relative Total
Energy vs. the Angle of Rotation for
DAPSC with One Semicarbazone "arm"
Locked Backward . .


viii


96


105


108




111




113









Figure 6-5


Figure 6-6


Figure 6-7


An Illustration of the Possible Spin
States for an Fe2* (d6) Ion .

Coordinate System and Atom Numbering
Scheme . .

A Representation of [Fe(DAPSC)(H20)2]2+
in the Optimum Geometry as Determined
by ZINDO ............


114


118



119















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

A SYNTHETIC, STRUCTURAL AND THEORETICAL INVESTIGATION
OF PENTADENTATE SCHIFF BASE LIGANDS

By

SHAUN O. SOMMERER

May 1991


Chairman: Dr. Gus J. Palenik
Major Department: Chemistry

The pentadentate Schiff base ligands 2,6-diacetyl-

pyridinebis(semicarbazone), DAPSC, 2,6-diacetylpyridine-

bis(benzoic acid hydrazone), DAPBAH, and 2,6-diacetyl-

pyridinebis-(acethydrazone), DAPATD, were used to isolate Sn *,

Ti3', and Cu2', respectively, in pentagonal bipyramidal, PBP,

geometry. The complexes were characterized by X-ray

diffraction studies, and the structural details of each

complex are reported and discussed. A unique Fe-DAPSC PBP

species is also reported which has been characterized by an X-

ray diffraction study, and evidence is put forth to show that

in one of the molecules, the Fe atom is formally 2+ where in

the other molecule the Fe atom is formally 3+.

Two PBP Cr3' complexes are reported which are markedly

distorted in the equatorial plane. Both structures have been

characterized by X-ray diffraction techniques and solution

x








magnetic moments show both species to be high spin d3

complexes. A group theoretical treatment of the possible spin

states resulting from the d3 configuration shows that a Jahn-

Teller distortion is possible in a D5h ligand field. The

equatorial distortion observed in both complexes is finally

shown to actually be a combination of effects, namely the

deprotonation of the ligand combined with a Jahn-Teller

distortion.

A theoretical study of the ligand DAPSC is presented

which employed several techniques. Molecular mechanics

calculations (MM2 type) (corroborated by MOPAC calculations)

showed that there were three configurations of the ligand

which corresponded to energy minima. Using the program ZINDO,

a complete geometry optimization of DAPSC was preformed, the

rotation barriers of the semicarbazone "arms" of DAPSC were

determined, and several geometry optimizations on a DAPSC

molecule perturbed by an Fe2* ion were preformed. The purpose

of these calculations was to determine the low energy

conformation of DAPSC as well as the effects of spin state

multiplicity on the geometry of both the ligand and the Fe-

DAPSC complex. The geometry and bond distances observed in

the optimized Fe-complex are in excellent agreement with what

has been observed in the solid state for a similar

[Fe(DAPSC)C12] complex as determined by X-ray diffraction

studies.















CHAPTER 1


INTRODUCTION



Seven-coordinate transition metal complexes are less

common since they cannot achieve as efficient a structural

form as the nearest coordination neighbors six and eight.

Moreover, in progressing from six to seven coordination, a

much less effective packing arrangement is achieved. Since

seven-coordination has, in the general case, a potential

surface that is not distinguished by a deep minimum

corresponding to one polytopal[l] form, the number of

monoisomorphic polyhedra with seven vertices is large (34)[2].

The pentagonal bipyramid (PBP), capped octahedron, and capped

trigonal prism are considered to be the three ideal polyhedra

for CN = 7 with PBP geometry, being the most common

arrangement found in monomers and dimers throughout the

periodic table(3]. The role of seven-coordination is

significant when viewed in the light of reaction intermediates

or transition states in associative reactions of 6-coordinate

complexes, oxidative addition reactions of 5-coordinate

complexes, and dissociative reactions of 8-coordinate

complexes[4]. Therefore, systematic investigations of 7-









2
coordinate complexes can provide added insight to these

important areas of chemistry.

A very efficient way of forming pentagonal bipyramidal

(PBP) complexes (C.N. = 7) is with pentadentate ligands that

can occupy the pentagonal plane, particularly if the ligand is

at least partly conjugated[5]. The two types of pentadentate

ligands that have been used successfully in this fashion to

achieve PBP geometry are either macrocyclic in nature or

noncyclic. A disadvantage of the macrocyclic type ligands is

that the size of the ligands central "hole" is of critical

importance in determining which metal-cations the ligand will

hold effectively. If the match between the metal-cation and

the "hole" size is incorrect, puckering of the pentagonal

girdle results causing distortion and possible instability.

Noncyclic pentadentate ligands on the other hand are not

hindered to the same extent by the metal-cation size

constraint since the "hole" is not bound on all sides;

consequently, this type of ligand is more versatile in

achieving PBP geometry as it can accommodate metal atoms of

different sizes by increasing the L-M-L angle not spanned by

a chelate ring. Accordingly, noncyclic pentadentate ligands

offer the potential for the development of a wide based

coordination chemistry due to the inherent flexibility of

these ligands.

In order to study seven-coordinate chemistry of the

transition metals a series of noncyclic pentadentate ligands









3

was designed which would consistently produce PBP geometry[6].

Three of these ligands are depicted in Figure 1.

DAPSC, DAPBAH, and DAPAAH have been used successfully to

produce several complexes which exhibit PBP geometry. DAPSC

especially has been found to react with virtually all +2 and

+3 ions of groups 3, 12, and 13 as well as the elements Ti to

Cu[6-16]. Although the usual result is PBP geometry, higher

coordination numbers are found with the larger +3 ions[13,14].

DAPBAH and DAPAAH mimic the coordination sites of DAPSC

but vary in the functional groups directed away from the

coordinated metal. With the replacement of the -NH2 function

of the acid hydrazide with either a -C6H5 function to give

DAPBAH, or a -CH3 function giving DAPATD, the solution

chemistry of the complex would be expected to change,

especially in terms of the solubility for a particular complex

in aqueous verses an organic media. Although DAPBAH and

DAPAAH have been used less extensively, previous results'5 have

demonstrated that these ligands are quite reactive with many

of the transition metals.

Several intriguing aspects concerning the chemistry and

structure of these pentadentate ligands emerged during the

initial investigation[6] which merited further examination.

As a consequence, a research project was designed to analyze

the coordination chemistry and structure of these ligands with

the following goals in mind: first, to advance the on going

study of seven-coordinate chemistry by preparing new seven-













CH3 N CH3


HNN NNH
HN DAPSC NH

NH2 0 0 NH2





CH3 CH3









N N



CH3 %{ CH3

N NNH

HN DAPAAH N

CH3 0 0' CH3





Figure 1-1. 2.6-diacetylpyridinebis(semicarbazone, (DAPSC),
2, 6-diacetylpyridinebis(benzoic acid hydrazone), (DAPBAH), and
2,6-diacetylpyridinebis(acethydrazone), (DAPAAH).









5

coordinate complexes of metals not yet isolated with the three

pentadentate ligands; second, to investigate further the

structural aspects of PBP complexes exhibiting unusual

distortions within the coordination sphere; third, to study

the structural characteristics of these pentadentate ligands;

and, finally, to explore the reaction chemistry observed with

these ligands. To accomplish this work, general laboratory

procedures were used for the synthesis with an emphasis on

obtaining single crystals for X-ray diffraction studies and

structural determination.

The following chapters report the experimental work which

was preformed and discuss what was learned regarding the

chemistry and structure of DAPSC, DAPBAH, and DAPAAH.













CHAPTER 2


PENTAGONAL BIPYRAMIDYL COMPLEXES OF Sn(IV), Ti(III),
AND Cu(II).



Introduction

The synthesis and structural characterization by X-ray

diffraction techniques of Sn(DAPSC)C122,, Ti(DAPBAH)CI1, and

Cu(DAPAAH)(H20)Cl' is addressed in this chapter. This set of

complexes demonstrates the versatility of the respective

ligands in the study of 7-coordinate chemistry since each of

these complexes was found to exhibit PBP geometry.

The PBP Sn(IV) complex was unexpectedly isolated from

aqueous solution during investigations involving

(CH4N)3[Pt(SnCl3)5]. This is a unique complex in that it is

the first example of a water soluble seven-coordinate Sn(IV)

complex in which a pentadentate ligand was used. With the

isolation of the Ti(DAPBAH)C12 complex, there is now an

example of each of the first transition series (i. e. Sc Zn)

in a PBP field coordinated by a pentadentate ligand. Finally,

this report of the Cu(DAPAAH)(H20)C1 complex marks the first

account of DAPAAH being used to isolate a Cu(II) ion in PBP

geometry.









7

Experimental

Materials. All materials and solvents were reagent grade

and used as supplied from the manufacturer except where noted.

Preparation of rSn(DAPSC)C1,1C1, 2H20 (I). Both

(CH3NH)3[Pt(SnCl3)s] (0.632g, 0.4 mmole) and DAPSC (0.113g, 0.4

mmole), prepared by methods previously described[9,17], were

slurried together in 40 mL of H20. HC1 was added drop-wise

until the pH = 1.00. As the solution cleared to a

yellow/brown color, a fine black precipitate was evident in

the solution. A dark yellow/brown solution void of black

precipitate was obtained after filtering through a fine glass

frit. Slow evaporation of the filtrate gave yellow crystals

within four days.

Preparation of Ti(DAPBAH)C*, (II). In a dry box with

an Argon atmosphere, TiCl3 (0.151g, 1.0 mmole) was weighed

out and placed into a dry Schlenk flask containing a magnetic

stirring bar. The flask was sealed with a rubber septum and

removed from the dry box. By means of a needle and syringe,

2,6-diacetylpyridine (0.168g, 1.0 mmole) dissolved in 20 mL

absolute ethanol was added to the flask. Next, benzoic acid

hydrazide (0.272g, 2.0 mmole) dissolved in 20 mL of absolute

ethanol was added by needle and syringe. The closed mixture

was stirred for three hours after which the solvent was

removed by vacuum. The Schlenk flask containing the dry crude

solid was placed back into the dry box and the rubber septum

was removed. Acetonitrile (30 mL), previously dried over









8

P2010, was added and the mixture was stirred for two hours.

The mixture was then filtered through a fine glass frit and a

clear dark red solution was obtained. The volume of this

solution was reduced to 13 mL and then placed into an

Erlenmyer flask, sealed, removed from the dry box, and placed

in a freezer (-10 *C). Air stable red single crystals were

obtained after three weeks.

Preparation of Cu(DAPAAH)Cl, (III). Acethydrazide

(0.156g, 2.0 mmole), CuC12 2H20 (0.170g, 1 mmole), and 2,6-

diacetylpyridine (0.168g, 1.0 mmole), were combined in 30 mL

of a 50/50 mixture of ethanol/water solution. This solution

was then heated to 580C and stirred for one-half hour. A dark

green solution was the result of this reaction which was then

filtered through a fine glass frit while warm. A crop of dark

green crystals were removed after eight days. The density of

these crystals was measured at 1.57 g/cm3 by floatation

techniques.

X-ray Crystallography. Crystals having the dimensions

0.15 x 0.17 x 0.23 mm, 0.18 x 0.20 x 0.25 mm, and 0.10 x 0.14

x 0.15 mm for I, II, and III, respectively, and suitable for

diffraction studies, were mounted on the end of a glass

fibers. All subsequent measurements for I and II were made

using a Nicolet R3m diffractometer with graphite-monochromated

Mo-Ka radiation (X = 0.71069A). For compound III, the

subsequent measurements were made using a Nicolet P1

diffractometer, up graded to R3m specifications, with









9

monochromated Cu-Ka radiation (X = 1.54056A) with a nickel

filter in place.

The cell dimensions for each of the three compounds were

determined by a least squares refinement of 25 automatically

centered reflections. A variable-speed (1" 29.3") 2e scan

technique was used to measure the intensity data from 0" to

50, 0* to 45, and 0 to 1100 in 28 for I, II, and III

respectively. Two standard reflections were measured every 98

reflections to monitor for any decomposition during the X-ray

analysis. No absorption corrections were made. The pertinent

crystal data is given in Table 2-1.

Structure Refinement. The data reduction, structure

solution and final refinement were performed using the NRCVAX

(PC-Version)[18] package of programs. The Sn, Ti and Cu atoms

and all non-hydrogen atoms were located by the heavy-atom

method (Patterson and Fourier syntheses) and refined

anisotropically by full-matrix least squares. The hydrogen

atoms were located using a difference Fourier map and refined

isotropically. The models converged to an R of 0.047, 0.061,

and 0.061 with Rw values of 0.061, 0.086, and 0.068 for I, II,

and III respectively. The final positional parameters for non-

hydrogen atoms are given in Tables 2-2 to 2-4. The final bond

distances involving the non-hydrogen atoms and bond angles are

listed in Tables 2-5 to 2-7 with the anisotropic thermal

parameters given in Tables 2-8 to 2-10. Tables 2-11 to 2-13

list the final positional parameters for the hydrogen atoms.




























H *












S-

"U,
















q -

u
o r--















0
N



a4
- H cE




o
-I.
'-U 3 ")
D (
H. C) C/)I


NoN V
no '- O
S .M '.0
* vO

CO00CT> CT


ON
"*
~r-1C


(Y0
~(V)
N3


o0
O
*
dr-1


.-C)

II)0
CO -0

\o
r-O 0o


4.)


00 0

0 0Q O
CO 0 0 a
Oi#< 5 1 3


:3: 0 -04 (a
E IQ X O ta.> N 0 M I)


0
N *L )
OO
a~cL 3


cH-o

^0 CO


?4~


0

( H- )-4
.0\


,-N
N *
C-


N

N






r,
C? '



PI
a


II



^Sl
cy


dcHo


4p

H
a)

cN
A
C


HZ M
- 0; O


vO t



















Table 2-2.


Atomic Parameters for I, x,y,z and Biso.
E.S.Ds. refer to the last digit printed.


x/a y/b z/c Biso


.7209
.7977
.6410
.5462
.5548
.8018
.9554
.8062
.4690
.6985
.7071
.4779
.5683
.9313
.9911
1.0211
1.1647
1.2383
1.1722
1.0287
.9410
1.0033
.5773
.7343
.8857
.6830
.6672


(1)
(3)
(3)
(6)
(7)
(7)
(7)
(8)
(10)
(7)
(9)
(10)
(10)
(10)
(13)
(9)
(10)
(10)
(10)
(10)
(10)
(12)
(10)
(10)
(11)
(3)
(3)


.8794
.7284
1.0346
.8820
.8033
.9612
.9285
.8419
.9221
.9660
.8016
.7322
.9225
.9952
1.0438
.9794
1.0122
.9893
.9348
.9064
.8556
.8258
.7790
.8522
.3283
.7146
1.0786


(1)
(2)
(2)
(5)
(5)
(5)
(5)
(5)
(7)
(6)
(6)
(7)
(7)
(7)
(10)
(6)
(7)
(8)
(8)
(6)
(6)
(8)
(6)
(7)
(8)
(2)
(2)


.1567
.2187
.1010
.2303
.0844
.2706
.1551
.0391
.3494
.3238
-.0146
-.0344
.2994
.2845
.3594
.2176
.2174
.1532
.0897
.0920
.0256
-.0488
.0140
.5155
.8452
.8170
.4759


(1)
(1)
(1)
(3)
(3)
(4)
(4)
(4)
(5)
(4)
(4)
(5)
(5)
(5)
(6)
(5)
(6)
(6)
(6)
(5)
(5)
(6)
(5)
(5)
(6)
(1)
(1)


2.01
3.3
3.14
2.7
2.9
2.1
2.1
2.2
3.5
2.6
2.8
3.3
2.5
2.6
3.8
2.3
3.0
3.4
3.0
2.5
2.3
3.0
2.5
4.6
6.4
4.1
3.9


Biso is the Mean of the Principal
Axes of the Thermal Ellipsoid


Sn
C11
C12
01
02
N3
N4
N5
N1
N2
N6
N7
Cl
C2
C3
C4
C5
C6
C7
C8
C9
C10
Cll
W1
W2
C13
C14


(2)
(1)
(9)
(2)
(3)
(3)
(3)
(3)
(4)
(3)
(3)
(4)
(3)
(3)
(5)
(3)
(4)
(4)
(4)
(3)
(3)
(4)
(3)
(4)
(5)
(1)
(1)
















Table 2-3.


Atomic Parameters for II, x,y,z and Biso.
E.S.Ds. refer to the last digit printed.


x/a y/b z/c Biso


.1286
.1899
.0230
.3430
.2329
.2837
.1449
-.0988
-.0443
.0077
.3824
.0297
.0332
-.1156
-.2559
-.3795
-.3661
-.2236
-.1859
-.3003
.1534
.5386
.6388
.7859
.8275
.7313
.5869
.2364
.1549
.236
.394
.4721
.3915


(2)
(4)
(4)
(8)
(8)
(11)
(11)
(10)
(12)
(13)
(12)
(13)
(17)
(13)
(16)
(15)
(15)
(15)
(14)
(22)
(15)
(12)
(12)
(14)
(14)
(16)
(12)
(16)
(17)
(3)
(3)
(19)
(17)


.5235
.3800
.6553
.5435
.6027
.4531
.4488
.4548
.5505
.6035
.5089
.4009
.3486
.4032
.3599
.3724
.4267
.4637
.5169
.5329
.6284
.5293
.5910
.6167
.5770
.5127
.4898
.6874
.7096
.7605
.7862
.7591
.7135


(2)
(2)
(2)
(5)
(5)
(8)
(7)
(6)
(7)
(7)
(8)
(8)
(12)
(8)
(9)
(12)
(11)
(9)
(10)
(14)
(9)
(7)
(9)
(10)
(11)
(10)
(9)
(8)
(10)
(13)
(11)
(10)
(9)


.2035
.1565
.2488
.2567
.1430
.3435
.2991
.2098
.1121
.0630
.3170
.3162
.3788
.2659
.2719
.2197
.1627
.1591
.1030
.0397
.0836
.3565
.3321
.3711
.4327
.4574
.4193
.0389
-.0248
-.0664
-.0466
.0186
.0605


(1)
(2)
(2)
(3)
(3)
(5)
(4)
(5)
(5)
(5)
(5)
(6)
(8)
(7)
(8)
(10)
(9)
(7)
(7)
(12)
(6)
(5)
(5)
(6)
(6)
(6)
(6)
(6)
(7)
(8)
(9)
(8)
(6)


3.83(9)
5.5 (2)
5.1 (2)
4.1 (3)
4.0 (3)
4.6 (5)
4.2 (4)
4.0 (4)
4.6 (5)
5.0 (5)
3.6 (5)
3.9 (5)
5.8 (7)
4.3 (6)
5.8 (7)
7.6 (9)
6.4 (8)
5.0 (6)
5.5 (7)
7.2 (9)
4.4 (6)
3.3 (5)
4.3 (6)
5.4 (7)
5.6 (7)
6.0 (7)
4.7 (6)
4.4 (6)
6.1 (7)
8.3 (9)
8.4 (9)
6.7 (8)
5.1 (7)


Biso is the Mean of the Principal
Axes of the Thermal Ellipsoid


Ti
Cll
C12
01
02
N1
N2
N3
N4
N5
Cl
C2
C3
C4
C5
C6
C7
C8
C9
C10
ClI
CA1
CA2
CA3
CA4
CA5
CA6
CB1
CB2
CB3
CB4
CB5
CB6


















Table 2-4.


Atomic Parameters for III, x,y,z and Biso.
E.S.Ds. refer to the last digit printed.


x/a y/b z/c Biso
i~~ ~ ~~ i ,i H ,IIIII


.2545
.5138
-.0564
.0241
.5683
.7701
.1665
.3326
.4056
.3539
.2438
.1379
.0872
.3925
.4543
.3546
.4052
.2987
.3011
.2461
.1891
.1900
.1312
.0735
.1030
.0396


(1)
(3)
(3)
(9)
(20)
(9)
(7)
(7)
(8)
(8)
(8)
(8)
(8)
(10)
(13)
(10)
(16)
(10)
(12)
(13)
(12)
(10)
(10)
(16)
(10)
(14)


.2823
.2839
.2043
.2864
.2810
.3874
.4146
.4122
.2911
.2213
.1128
.2276
.3007
.3899
.4662
.1255
.0797
.0628
-.0427
-.0911
-.0389
.0662
.1328
.0917
.3971
.4767


(1)
(2)
(2)
(5)
(10)
(5)
(4)
(4)
(5)
(5)
(4)
(4)
(5)
(6)
(10)
(6)
(10)
(6)
(7)
(6)
(6)
(6)
(6)
(8)
(6)
(8)


.0028
.0733
-.2091
-.0570
.7348
-.0181
.0634
-.0641
-.1383
-.0918
.0035
.0964
.1405
-.1174
-.1661
-.1060
-.1718
-.0501
-.0488
.0069
.0612
.0584
.1132
.1781
.1167
.1616


(1)
(1)
(1)
(4)
(7)
(5)
(3)
(3)
(3)
(3)
(4)
(3)
(3)
(4)
(6)
(4)
(6)
(4)
(6)
(6)
(5)
(4)
(4)
(5)
(4)
(5)


2.75(5)
4.21(9)
5.8 (1)
4.1 (3)
8.1 (7)
6.0 (4)
3.5 (3)
3.9 (3)
3.5 (3)
3.1 (3)
3.2 (3)
3.0 (3)
3.3 (3)
3.4 (4)
5.0 (5)
3.5 (4)
5.4 (6)
3.2 (4)
4.2 (4)
4.5 (4)
4.1 (5)
3.1 (3)
3.3 (3)
5.0 (5)
3.1 (4)
4.3 (4)


Biso is the Mean of the Principal
Axes of the Thermal Ellipsoid


Cu
C11
C12
Wl
W2
W3
01
02
N1
N2
N3
N4
N5
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
Cll
C12
C13
















Table 2-5. Bond Distances(A) and Angles(*) for I


2.354(2)
2.368(2)
2.127(5)
2.123(6)
2.272(7)
2.260(7)
2.259(6)
1.282(10)
1.267(10)
1.371(9)
1.277(12)
1.348(10)
1.347(10)
1.336(10)


C9
Cl
Cl
Cll
ClI
C3
C4
C5
C6
C7
C8
C9
C10


1.297(11)
1.304(11)
1.360(12)
1.367(12)
1.322(12)
1.479(13)
1.477(12)
1.395(12)
1.368(14)
1.386(14)
1.381(13)
1.481(13)
1.484(12)


C11-Sn-C12
Cll-Sn-01
Cll-Sn-02
Cll-Sn-N3
Cll-Sn-N4
Cll-Sn-N5
C12-Sn-01
C12-Sn-02
C12-Sn-N3
C12-Sn-N4
C12-Sn-N5
01-Sn-02
01-Sn-N3
01-Sn-N4
01-Sn-N5
02-Sn-N3
02-Sn-N4
02-Sn-N5
N3-Sn-N4
N3-Sn-N5
N4-Sn-N5
Sn-01-Cl
Sn-02-C11
Sn-N3-N2
Sn-N3-C2
N2-N3-C2
Sn-N4-C4
Sn-N4-C8


176.94(8)
88.1(2)
90.6(2)
88.8(2)
90.5(2)
94.8(2)
89.6(2)
90.9(2)
88.6(2)
90.0(2)
88.2(2)
78.4(2)
72.8(2)
141.4(2)
149.7(2)
151.1(2)
140.3(2)
71.5(2)
68.6(2)
137.3(2)
68.9(2)
118.3(5)
119.1(6)
112.5(5)
123.3(5)
124.1(7)
119.6(5)
119.9(6)


C4-N4-C8
Sn-N5-N6
Sn-N5-C9
N6-N5-C9
N3-N2-C1
N5-N6-C11
01-C1-N1
01-C1-N2
N1-C1-N2
N3-C2-C3
N3-C2-C4
C3-C2-C4
N4-C4-C2
N4-C4-C5
C2-C4-C5
C4-C5-C6
C5-C6-C7
C6-C7-C8
N4-C8-C7
N4-C8-C9
C7-C8-C9
N5-C9-C8
N5-C9-C10
C8-C9-C10
02-C11-N6
02-C11-N7
N6-C11-N7


120.4(7)
114.3(5)
123.0(6)
122.7(7)
115.5(7)
114.4(7)
121.8(8)
120.9(7)
117.4(8)
125.2(8)
113.1(7)
121.7(8)
115.2(7)
120.8(8)
124.0(8)
118.4(9)
121.0(9)
118.3(8)
121.1(8)
114.8(8)
124.0(8)
113.1(7)
124.5(8)
122.4(8)
120.2(8)
122.1(9)
117.7(8)


Cll
C12
01
02
N3
N4
N5
Cl
Cll
N2
C2
C4
C8
N6














Table 2-6. Bond Distances(A) and Angles(*) for II


Cll
C12
01
02
N2
N3
N4
C1
C11
N2
Cl
C2
C4
C8
N5
C9
Cll
CA1
C3
C4


Cll-Ti-C12
Cll-Ti-01
Cll-Ti-02
Cl1-Ti-N2
C11-Ti-N3
C11-Ti-N4
C12-Ti-01
C12-Ti-02
C12-Ti-N2
C12-Ti-N3
C12-Ti-N4
01-Ti-02
01-Ti-N2
01-Ti-N3
01-Ti-N4
02-Ti-N2
02-Ti-N3
02-Ti-N4
N2-Ti-N3
N2-Ti-N4
N3-Ti-N4
Ti-01-Cl
Ti-02-C11
N2-N1-C1
Ti-N2-N1


2.322(4)
2.316(4)
1.982(7)
1.983(7)
2.179(9)
2.205(9)
2.188(9)
1.298(12)
1.320(14)
1.361(13)
1.336(14)
1.295(14)
1.373(17)
1.351(16)
1.377(16)
1.289(17)
1.296(17)
1.464(14)
1.459(19)
1.463(16)

169.9(2)
95.0(2)
93.9(2)
88.1(3)
85.2(2)
88.4(3)
93.8(2)
93.0(2)
89.9(3)
84.7(2)
86.6(3)
77.0(3)
71.4(3)
141.2(3)
149.3(4)
148.4(3)
141.7(3)
72.3(4)
69.8(4)
139.3(4)
69.4(4)
121.1(6)
119.7(7)
107.9(8)
118.2(7)


C4
C5
C6
C7
C8
C9
C11
CA1
CA1
CA2
CA3
CA4
CA5
CBI
CB1
CB2
CB3
CB4
CB5


- C5
- C6
- C7
- C8
- C9
- C10
-CB1
- CA2
- CA6
- CA3
- CA4
- CA5
- CA6
- CB2
- CB6
- CB3
- CB4
- CB5
- CB6


N1-C1-CA1
N2-C2-C3
N2-C2-C4
C3-C2-C4
N3-C4-C2
N3-C4-C5
C2-C4-C5
C4-C5-C6
C5-C6-C7
C6-C7-C8
N3-C8-C7
N3-C8-C9
C7-C8-C9
N4-C9-C8
N4-C9-C10
C8-C9-C10
02-C11-N5
02-C11-CB1
N5-C11-CB1
C1-CAl-CA2
C1-CA1-CA6
CA2-CA1-CA6
CA1-CA2-CA3
CA2-CA3-CA4
CA3-CA4-CA5


1.377(16)
1.368(24)
1.40(3)
1.346(20)
1.442(22)
1.486(22)
1.498(18)
1.374(15)
1.378(15)
1.413(15)
1.354(18)
1.376(19)
1.377(16)
1.386(17)
1.378(20)
1.38(3)
1.39(3)
1.42(3)
1.349(20)


118.8(9)
126.5(11)
113.8(10)
119.8(10)
112.4(9)
121.9(12)
125.7(12)
116.7(14)
122.4(12)
117.6(13)
122.1(14)
112.6(11)
125.3(13)
114.7(11)
122.1(17)
123.3(15)
122.2(11)
118.3(11)
119.5(11)
120.0(9)
121.4(9)
118.6(9)
121.2(10)
118.1(11)
121.7(10)
































Table 2-6 (cont.)


Ti-N2-C2
N1-N2-C2
Ti-N3-C4
Ti-N3-C8
C4-N3-C8
Ti-N4-N5
Ti-N4-C9
N5-N4-C9
N4-N5-C11
01-C1-N1
01-C1-CAI


123.7(8)
118.1(9)
120.2(7)
120.6(9)
119.2(10)
116.3(7)
122.6(10)
121.1(11)
109.5(10)
121.2(9)
120.0(9)


CA4-CA5-CA6
CA1-CA6-CA5
C11-CB1-CB2
C11-CB1-CB6
CB2-CB1-CB6
CB1-CB2-CB3
CB2-CB3-CB4
CB3-CB4-CB5
CB4-CB5-CB6
CB1-CB6-CB5


119.4(11)
121.0(11)
117.9(12)
119.7(10)
122.3(12)
117.0(14)
122.1(14)
118.4(14)
119.8(15)
120.3(12)























Table 2-7. Bond Distances(A) and Angles(*) for III


Cll
W1
01
02
N2
N3
N4
C12
C1
N2
01
C3
C5
C9


Cll-Cu-Wl
N2-N1-C1
N1-N2-C3
C5-N3-C9
N5-N4-C10
N4-N5-C12
02-C1-N1
02-C1-C2
N1-C1-C2
N2-C3-C4
N2-C3-C5
C4-C3-C5
N3-C5-C3
N3-C5-C6


2.270(2)
1.996(7)
2.264(5)
2.280(5)
2.216(6)
2.250(6)
2.239(6)
1.217(9)
1.213(10)
1.381(9)
1.377(11)
1.299(10)
1.337(10)
1.332(10)


177.5(2)
114.4(6)
121.0(6)
122.6(6)
120.4(6)
114.2(6)
121.7(7)
123.5(9)
114.8(8)
125.4(9)
113.3(7)
121.3(8)
115.7(7)
119.2(8)


N4 N5
N4 C10
N5 C12
Cl C2
C3 C4
C3 C5
C5 C6
C6 C7
C7 C8
C8 C9
C9 C10
C10 C11
C12 C13


C3-C5-C6
C5-C6-C7
C6-C7-C8
C7-C8-C9
N3-C9-C8
N3-C9-C10
C8-C9-C10
N4-C10-C9
N4-C10-C11
C9-C10-C11
01-C12-N5
01-C12-C13
N5-C12-C13


1.378(9)
1.300(10)
1.367(10)
1.501(14)
1.491(13)
1.466(12)
1.400(12)
1.360(16)
1.371(15)
1.395(11)
1.490(11)
1.476(12)
1.491(12)


125.1(8)
118.7(8)
121.5(8)
118.2(9)
119.8(7)
116.0(6)
124.2(8)
112.0(7)
126.1(8)
121.9(8)
121.4(7)
123.8(7)
114.8(7)






















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Table 2-11. Hydrogen Atomic Parameters x,y,z and Biso for
I. E.S.Ds. refer to the last digit printed.



x/a y/b z/c Biso

H1(N1) .397 (12) .910 (8) .339 (6) 3.2
H2(N1) .489 (11) .955 (7) .385 (5) 3.2
H3(N2) .711 (11) 1.017 (7) .368 (5) 3.2
H4(C3) .956 (11) 1.026 (8) .405 (6) 3.2
H5(C3) 1.092 (12) 1.014 (7) .373 (5) 3.2
H6(C3) 1.013 (11) 1.110 (8) .349 (5) 3.2
H7(C5) 1.209 (11) 1.047 (7) .261 (6) 3.2
H8(C6) 1.355 (11) 1.007 (7) .154 (5) 3.2
H9(C7) 1.238 (11) .914 (7) .051 (5) 3.2
H10(C10) 1.072 (12) .865 (8) -.063 (6) 3.2
H11(C10) .931 (11) .811 (7) -.096 (6) 3.2
H12(C10) 1.030 (11) .756 (8) -.046 (5) 3.2
H13(N6) .742 (11) .774 (8) -.055 (6) 3.2
H14(N7) .483 (12) .728 (8) -.073 (6) 3.2
H15(N7) .395 (12) .720 (8) -.009 (6) 3.2
H16(W1) .694 (12) .847 (8) .556 (6) 3.2
H17(W1) .741 (11) .921 (8) .512 (6) 3.2




Biso is the Mean of the Principal
Axes of the Thermal Ellipsoid


















Table 2-12. Hydrogen Atomic
for II. E.S.Ds. refer to


Parameters x,y,z and Biso
the last digit printed.


x/a y/b z/c Biso


H1(C3) .144 (13) .357 (8) .401
H2(C3) .011 (12) .374 (8) .402
H3(C3) .017 (12) .262 (8) .382
H4(N1) .265 (12) .510 (8) .370
H5(C6) -.264 .314 .314
H6(C6) -.491 .336 .220
H7(C7) -.470 .438 .127
H8(C10) -.361 (17) .564 (10) .041
H9(C10) -.349 (12) .471 (8) .022
H10(CO0) -.288 (13) .570 (8) -.002
H11(CA2) .607 .618 .281
H12(CA3) .868 .662 .352
H13(CA4) .936 .600 .465
H14(CA5) .767 .482 .507
H15(CA6) .509 .442 .439
H16(CB2) .033 .690 -.039
H17(CB3) .177 .785 -.115
H18(CB4) .453 .829 -.079
H19(CB5) .597 .774 .036
H20(CB6) .446 .693 .111



Biso is the Mean of the Principal
Axes of the Thermal Ellipsoid


(5)
(5)
(5)
(5)




(8)
(5)
(5)


4.7
4.7
4.7
4.7
4.7
4.7
4.7
4.7
4.7
4.7
4.7
4.7
4.7
4.7
4.7
4.7
4.7
4.7
4.7
4.7
















Table 2-13. Hydrogen Atomic Parameters x,y,z and Biso
for III. E.S.Ds. refer to the last digit printed.



x/a y/b z/c Biso

H1(C2) .362 .493 -.179 4.7
H2(C2) .531 .465 -.161 4.7
H3(N1) .461 .275 -.188 4.7
H4(C4) .347 .096 -.204 4.7
H5(C4) .517 .088 -.184 4.7
H6(C4) .381 .001 -.174 4.7
H7(C6) .340 -.064 -.083 4.7
H8(C7) .247 -.150 .005 4.7
H9(C8) .141 -.061 .092 4.7
H1O(C11) -.054 .097 .185 4.7
H12(C11) .113 .031 .182 4.7
H13(C11) .120 .127 .220 4.7
H14(N5) .022 .215 -.317 4.7
H15(C13) .138 .509 .170 4.7
H16(C13) -.028 .454 .195 4.7
H17(C13) -.041 .503 .134 4.7
H18(W1) -.041 .297 -.045 4.7
H19(W1) .005 .275 -.096 4.7
H20(W2) .568 .293 .700 4.7
H21(W2) .569 .235 .745 4.7
H22(W3) .664 .370 .005 4.7
H23(W3) .750 .384 .034 4.7


Biso is the Mean of the Principal
Axes of the Thermal Ellipsoid












27

Results and Discussion

Sn(DAPSC)C122 The crystals were found to contain

monomeric Sn(DAPSC)C1,22 cations and display PBP geometry which

is easily seen in Figure 2-1. Surprisingly, the complex was

obtained from aqueous solution and is very water soluble since

all related compounds[19-21] were isolated from organic media.

Oxidation of Sn2 to Sn4 is known[21] to occur in aqueous

solutions exposed to the air and has been observed to occur in

a structurally similar complex[19]. Indeed, a similar

oxidation has occurred in this instance. As noted above, a

fine black precipitate fell out as the solution cleared, which

suggests that a reduction of the Pt2 starting material to Pto

occurred. Whether or not this was a direct result of the Sn

oxidation is not clear. This is the first example of a metal

oxidation taking place in the presence of DAPSC and being

stabilized by the ligand. DAPSC tends to have a more reducing

nature as is observed in the Fe2' and Co2+ systems[6].

Compounds such as (CH3NH)3[Pt(SnCl3)s] and Pt(II)/Sn(II)

mixtures have been of interest for some time due to the

observed capability of these species to homogeneously catalyze

the hydroformylation, carbonylation, and hydrogenation

reactions[22]. Common to most of the discussion regarding

possible mechanisms for these reactions is the postulated

presence of free SnClI- ions in solution liberated by ligand

dissociation. The [Pt(SnCl3)5]3- species has long-term



















C6
C7
C5
C10 C7 C4 Cl

C9

N6 N N4 C2 C3
Cll
Sn N3
N7 N2
02
01
Ol Cl

C12
Nl







Figure 2-1. An ORTEP representation of Sn(DAPSC)C1,












29

stability in the presence of protic solvents, although in HCl

solutions metallic Pt is slowly precipitated[23] as we also

observed. Hence, in a HCl solution of (CH3NH)3[Pt(SnCl3)5]

with pH = 1.00 the concentration of free SnCl3" is probably

quite high and the likely source of the Sn atom for

coordination by DAPSC. Attempts to prepare the title complex

in good yield directly from SnCl2 2H20 and DAPSC in HC1 and

methanol/H20 solutions failed even when excess halide was

added in the form of KC1 which promotes[24] the formation of

SnCl3,

The geometry about the Sn-cation can be described as a

slightly distorted pentagonal bipyramid. A slight distortion

is apparent in the pentagonal equatorial plane as evidenced by

the lengths of the respective sides 01-02 2.685(7), 01-N3

2.611(8), N3-N4 2.553(9), N4-N5 2.555(9), and N5-02 2.560(9)A.

The axial chlorides also contribute to the observed distortion

since they are not exactly linear and make an angle of

176.94(8). A least-squares plane drawn through the five

coordinating atoms in the equatorial girdle shows little

deviation from planarity with the average of the deviations

being 0.034(7)A. The Sn ion can be considered to lie in the

equatorial plane since it deviates only 0.019(3)A out of the

plane made by the five equatorial donors. Dimensions within

the neutral ligand are similar to those observed in related

structures with no irregularities. There is evidence of












30
several hydrogen-bonds with in the asymmetric unit. Most

notable are the interactions between N2 C14, N6 C13, and

N7 W1 with distances (H *** Cl) of 2.053(10), 2.289(10), and

1.863(10)A with bond angles of 152(1), 143(1), and 156(1)"

respectively.

The two Sn Cl distances appear to be significantly

different, to = 4.09[25], although they appear to be

chemically equivalent. However an analysis of the various

intermolecular contacts involving Cll and C12 indicates that

the two Cl atoms have slightly different environments which

could account for the small but significant difference. The

Sn Cl distances are slightly shorter than that of 2.395(7)

and 2.387(7)A found in [Sn(dappc)Cl2]2' [20]. However the Sn -

O and Sn -N distances are slightly longer than in the

[Sn(dappc)Cl2]2* complex which suggests that the Sn Cl

distance may be influenced by non bonded interactions. The

much longer Sn Cl bond distance of 2.446(3)A when the trans

atom is carbon suggests a trans influence may be operative in

Sn compounds. The Sn Cl distance of 2.362(4)A in

tris(tropolonato)monochlorotin(IV) chloroform solvate[26]

would support this view. Unfortunately, there are not a

sufficient number of seven-coordinate Sn(IV) complexes for a

detailed comparison.

It has been suggested[27] that tin in a seven-coordinate

environment prefers pentagonal bipyramidal geometry; however,












31

our result may be attributed to the planar pentadentate nature

of the ligand rather than any stereochemical preference by the

metal[3].

Ti(DAPBAH)C1, The pentagonal bipyramidyl nature of this

complex is easily seen in Figure 2-2. With the isolation of

this complex, there are now examples of each of the first row

transition metals (Sc Zn) in PBP geometry coordinated in

part by planar pentadentate ligands. Seven coordinate Ti

complexes are known though most involve combinations of mono-

and bidentate ligands to arrive at a coordination number of

seven. This complex is unique in that a pentadentate ligand

has been used.

Preliminary experiments demonstrated that DAPSC does

indeed react with TiCl3, however crystalline products were

never evident in any of the reaction mixtures. Combining our

experience from previous experiments which have shown that

DAPSC works best in aqueous or semiaqueous solution together

with the fact that TiCl3 is extremely sensitive to water

suggested that neither this ligand or this solvent system

would be favorable for an attempt to obtain a PBP complex of

Ti3+. However, due to the high solubility of benzoic acid

hydrazide in organic media, the ligand DAPBAH emerged as a

better choice and the best of the three pentadentate ligands

to use for a reaction with Ti3.

The ligand DAPBAH is not as soluble in pure ethanol as












32



CB5

C10
~CB6
CB4 CB6 N5
C9
COl C8 C2
C7
CB3 CB1 N4

CB2 02 C12 C6







CA33
Ti N3 C5
C4

01 C2l C2
N2
Cl
CA6 C3
N1
CAl
CA5
CA2

CA3
CA4





Figure 2-2. An ORTEP representation of Ti(DAPBAH)C1,












33

are 2,6-diacetylpyridine and benzoic acid hydrazide

separately. Consequently, the complex had to be prepared by

a template type reaction rather than by combining the ligand

directly with Ti3'. Although two equivalents of water were

produced in the reaction forming the Schiff base ligand, no

deleterious results were detected in the course of the

reaction.

The Ti-cation can be described as being at the center of

a distorted pentagonal bipyramid with distortions occurring in

both the equatorial plane and axial positions. The distortion

observed in the equatorial plane has two contributions: first

and foremost is the formation of a monoanion resulting from

the deprotonation of the ligand at N1. Upon deprotonation,

the entire side of the ligand becomes conjugated as well as

negatively charged. The 3+ center now has a stronger

attraction to this side of the ligand as is evidenced in the

shorter Ti-N2 bond of 2.179(9)A verses the Ti-N4 bond of

2.188(9)A. Similarly, the distance between 01 and N2 in the

pentagonal plane is 2.434(9)A verses a distance of 2.188(9)A

from 02 to N4. The shorter side reflects a contraction in

that "arm" of the ligand due to the conjugation and increased

attraction towards the cationic center. The second

contribution to the distortion is a minor Jahn-Teller effect

due to the degeneracy of the possible electron configurations

for a d' species in a PBP field. Since the orbitals












34

potentially occupied by the single d-electron are not strongly

bonding, the distortion resultant from this effect is small.

Distortions due to the Jahn-Teller effect and the formation of

monoanions in these types of complexes will be examined at

length and in greater detail in chapter four.

An angle of 169.86(15)*, significantly less than the

expected 1800, is made by the atoms Cl1 Ti C12. Since

there appears to be no other intermolecular contacts between

the axial Cl's and other molecules in the asymmetric unit, the

distortion must be the result of an intermolecular electronic

effect. Pentadentate ligands of this type are known to have

some inherent flexibility especially between the "arms". This

complex provides an excellent example of this as illustrated

by the deviations of 01 and 02 from the least squares plane

calculated for Ti, N2, N3, and N4. All four of these atoms

show deviations of less than 0.002(9)A but 01 deviates

+0.051(8)A and 02 deviates -0.010(8)A. In essence, DAPBAH has

twisted slightly with one oxygen moving up and the other down

perpendicular to the equatorial plane. The electronic effects

from the two oxygens is the most likely contributor to the

axial distortion since the associated electron density would

repel the axial chloride ions to some degree.

Cu(DAPAAH)(H20)Cl' The crystals were found to contain

monomeric Cu(DAPAAH)(H20)C1l cations which display PBP geometry

as can be seen in Figure 2-3. Although the axial ligands


















C13


C11


An ORTEP representation of Cu(DAPAAH)C1(H20)*


Figure 2-3.












36
differ (i.e. one Cl- and one HO2) there appears to be no

disorder occurring. The geometry about the Cu-cation can be

described as being a somewhat disordered pentagonal bipyramid.

The distortion is apparent in the pentagonal equatorial plane

as evidenced by the length of the 01-02 side being 2.921(7)A

while the other four sides average length is 2.574(8)A

0.022(8). This distortion apparently does not affect the

planarity of the equatorial plane since a least-squares plane

drawn through the five coordinating atoms comprising the

equatorial plane shows that there is little deviation from

planarity with average deviations of 0.031(8)A out of the

plane for the five equatorial atoms. The Cu ion can be

considered to lie in the equatorial plane since it deviates

only 0.061(3)A out of the plane.

The bond lengths exhibited both within the coordination

sphere and throughout the ligand are very nearly the same as

those found in the previously reported [Cu(DAPSC)Cl(H20)]*

complex[16]. The major difference is found in the replacement

of an axial Cl- with a H20 molecule. An uncoordinated Cl- is

closely associated with the cation through a hydrogen bond to

the axial H20 with a O-H ... Cl distance of 2.30(3)A. There

also appears to be some interaction between the two

uncoordinated H20 molecules found in the asymmetric unit and

the axial Cl- with the closest contact being a hydrogen bond

between W3 and Cll with a O-H ..* Cl distance of 2.20(3)A.












37

Attempts to isolate IV by a similar method to the

aforementioned complex ([Cu(DAPSC)Cl(H20)]*) from a pure

aqueous solution failed due to the insolubility of the 2,6-

diacetylpyridine. In other experiments where the DAPAAH

ligand was prepared separately and then reacted with the Cu

ion, solubility problems were again encountered in pure

aqueous media though upon the addition of either ethanol or

methanol to the aqueous solution, the reaction appeared to

progress rapidly and clear dark green solutions were obtained.

The Cu(DAPAAH)C1H20' crystals were found to be much more

soluble in ethanol, methanol and ethanol/water solutions than

in pure H20. This observations suggest that the methyl groups

directed outward from the complex have an effect to some

extent on the solubility of this complex.
















CHAPTER 3

A NOVEL PENTAGONAL BIPYRAMIDAL IRON COMPOUND:
UNCONNECTED Fe(II) AND Fe(III) MOLECULES WITHIN
THE SAME ASYMMETRIC UNIT.



Introduction

In the preceding chapter it was noted that the ligand

DAPSC reacts with all the metals of the first transition

series and that in each case the result has usually been the

formation of seven-coordinate complexes displaying PBP

geometry. A particularly interesting system which we have

come upon in this series is that of the iron-DAPSC complexes.

Fe(II)[7] and Fe(III)[9] cations coordinated by DAPSC

have been isolated and structurally characterized by means of

X-ray structure studies. Both compounds were obtained from

the same reaction mixture. However, in addition to these two

compounds, a third product was isolated from the same reaction

mixture which appeared to have a different crystal habit than

the two compounds previously characterized. In order to

determine the composition of the third product, an

investigation of the crystal structure by means of an X-ray

analysis was undertaken.

Previous attempts at determining the structure of this

product were unsuccessful. Thus, a more detailed experimental

38












39
section outlining the crystallographic work is presented in

addition to the normal experimental details.



Experimental

Materials. All chemicals were reagent grade and used as

supplied.

Preparation of [Fe(DAPSC)Cl H2012'/3. DAPSC (0.5546g, 2

mmole) prepared by the method previously described[9] was

combined with FeCl3 H20 (0.5406g, 2 mmole) in 50 mL deionized

H20. The pH was lowered to 1.00 with HC1 and stirred for 1.5

hours. A deep red solution resulted which was filtered and

allowed to slowly evaporate. After 16 days the product was

obtained, the second of two red products. The first red

product, the Fe(III)-DAPSC, formed red needles some of which

were quite long. The second product was dark red "chunks"

which are easily distinguishable from the first red product.

No green product (Fe(II)) was visible at this point.

Crystallography. A dark red crystal suitable for an X-

ray study having the dimensions 0.18 x 0.21 x 0.25 mm was

mounted on the end of a glass fiber. All subsequent

measurements were made using a Nicolet R3m diffractometer with

graphite-monochromated Mo-Ka radiation (X = 0.71069A). The

cell dimensions were determined by a least squares refinement

of 25 automatically centered reflections in the 28 range 3.63*

- 24.56*. A variable-speed (1 29.3*) 28 scan technique












40

was used to measure the intensity data from 2.0* to 46.00

degrees in 28 corresponding to hkl values of 0 to 10, 0 to 18,

and -22 to 22 respectively. Two standard reflections were

measured every 98 reflections to monitor for any decomposition

during the X-ray analysis. No absorption correction was made.

There were 2543 unique reflections measured of which 2473 with

an Inet > 2.5a(Inet) were used in the analysis. The density

of the compound was found to be 1.68 g/cm3 by flotation which

when taken together with the unit cell volume of 1808.4 A3

suggested that there were four molecules per unit cell

assuming a molecular weight of -450 g/mole. From an analysis

of the systematic absences, either of the space groups P21 or

P21/m were possible though from an evaluation of the intensity

statistics P 21 appeared to be the best choice. The data

reduction, structure solution and final refinement were

performed using the NRCVAX (PC-Version)[18] package of

programs. The Fe atoms and all non-hydrogen atoms were located

by the heavy-atom method (Patterson and Fourier syntheses) and

refined anisotropically by full-matrix least squares. The

hydrogen atoms were located using a difference Fourier map and

refined isotropically. The model converged to an R of 0.036

and a Rw of 0.039. The largest shift/e.s.d. in the last cycle

was 0.213. A final difference fourier synthesis had a maximum

peak of 0.530 and a minimum peak of -0.560 e A-3 and was

featureless.












41

Results and Discussion

As noted previously, the structural solution for this

compound was somewhat involved. The direct method routines of

both the SHELXTL[28] and NRCVAX (PC-version)[18] software

packages failed to arrive at a reasonable initial solution for

this compound. This is often the case when noncentrosymmetric

crystals are encountered and caution must be exercised when

using "black-box" solving routines in these situations. We

were eventually able to arrive at an initial solution for the

structure by locating the Fe atoms from a Patterson map though

with two heavy atoms in the asymmetric unit, four Fe vectors

resulted which had to be properly sorted out. Upon the

correct phasing of the Fe atoms, the positions of the

remaining non-hydrogen atoms were easily determined from

subsequent Fourier syntheses.

The refinement of this model proceeded smoothly and the

resulting structural parameters contained nothing irregular or

abnormal. To check if any symmetry elements had been

overlooked, the program MISSYM which is part of the NRCVAX

(PC-version)[18] software package was run using the atomic

parameters from the final model. MISSYM checks the structural

data and can detect possible missing symmetry which may have

been described in the wrong space group. Upon running the

program no additional symmetry was detected. This result

together with the smooth refinement and intensity statistics













42

which indicated a noncentrosymmetric structure confirms that

P21 was indeed the correct space group for this structure.

The PBP nature of the two cations is easily seen in

Figure 3-1. The final atom coordinates are given in Table 3-1

and bond distances and angles are given in Table 3-2. The

final anisotropic thermal parameters are given in Table 3-3

and the final coordinates for the hydrogen atoms are provided

in Table 3-4.

The presence of only five anions in the asymmetric unit

implies that one Fe-cation is formally 2+ and the other 3+

which is highly unusual indeed. The possibility does exist

that an additional anion is present in the form of a

deprotonated ligand or water molecule though this is doubtful

for several reasons. First the hydrogen atoms bonded to N2,

N6, N9, and N13 are known to be acidic and it has been pointed

out previously that DAPSC can in fact undergo deprotonation at

one of these sites with the semicarbazone arm then acting as

monoanion and carrying an overall negative charge[29].

However, all hydrogen atoms associated with the ligand were

clearly found in a Fourier difference map, so both ligands are

fully protonated and neither has undergone deprotonation.

Second, the two coordinated and two uncoordinated H20

molecules in the asymmetric unit could have undergone

deprotonation leaving a OH- anion, but this is highly unlikely

since the compound was isolated from a highly acidic solution.

























02 4 N8
C22 C12
N13 Fe2

N12 N9
C20 C12 N10
C21 C1, 3 C7 C6
C19l N11 C4
C15 C5
C18 C16 C4

C9 N4 C2 C3
C17

N7 N5
N3
N6

Cll Fe
N7 02 01 C 1


Figure 3-1. An ORTEP representation of the
Fe(II/III)-DAPSC complex.














Table 3-1. Atomic Parameters x,y,z and Biso.
E.S.Ds. refer to the last digit printed.


x y z Biso


.1524
.7548
-.1406
.4228
.4227
1.0449
.0447
.1719
.7544
.8690
-.0908
.0321
.1013
.2433
.2733
.2788
.2180
.7272
.6466
.6521
.7067
.8358
.9052
1.0061
-.0050
.1388
.1115
.2181
.2617
.3267
.3479
.3061
.3239


(2)
(2)
(3)
(3)
(7)
(7)
(8)
(8)
(8)
(8)
(11)
(10)
(9)
(9)
(9)
(10)
(9)
(10)
(9)
(9)
(9)
(9)
(10)
(11)
(12)
(11)
(12)
(10)
(11)
(13)
(13)
(11)
(10)


.5000
.3115
.5035
.2893
.5049
.3208
.4731
.3534
.4630
.3369
.5284
.6291
.6352
.6140
.4439
.3485
.2136
.6005
.4637
.3683
.1979
.1770
.1815
.2766
.5408
.7130
.8065
.7030
.7761
.7563
.6663
.5953
.4943


Fel
Fe2
Cll
C12
W1
W2
01
02
03
04
N1
N2
N3
N4
N5
N6
N7
N8
N9
N10
N11
N12
N13
N14
Cl
C2
C3
C4
C5
C6
C7
C8
C9


.4175
1.0514
.4685
1.1062
.3735
1.0112
.3098
.4064
1.0598
1.1652
.2036
.2918
.3612
.4912
.5226
.5263
.4631
.9984
.9388
.9450
.9716
1.1038
1.1759
1.2710
.2689
.3923
.3571
.4682
.5166
.5884
.6113
.5608
.5780


(1)
(1)
(1)
(1)
(3)
(3)
(3)
(3)
(3)
(3)
(4)
(4)
(3)
(3)
(3)
(4)
(4)
(4)
(4)
(3)
(3)
(3)
(3)
(4)
(4)
(4)
(5)
(4)
(5)
(5)
(5)
(4)
(4)


1.8 (4)
1.8 (4)
2.8 (8)
2.6 (8)
2.9 (2)
2.8 (2)
2.4 (2)
2.2 (2)
2.6 (2)
2.8 (2)
3.3 (3)
2.3 (3)
1.9 (3)
2.1 (3)
2.2 (3)
2.3 (3)
2.3 (3)
2.7 (3)
2.3 (3)
1.9 (2)
1.8 (3)
2.0 (3)
2.4 (3)
3.4 (3)
2.4 (3)
2.0 (3)
2.8 (3)
1.9 (3)
2.6 (4)
3.2 (4)
3.0 (4)
2.1 (3)
2.1 (3)


(1)
(2)
(1)
(4)
(4)
(3)
(3)
(4)
(4)
(5)
(4)
(4)
(4)
(4)
(5)
(4)
(5)
(4)
(4)
(4)
(4)
(4)
(5)
(6)
(5)
(6)
(5)
(6)
(6)
(6)
(5)
(6)






















Table 3-1 (cont.).


x y z Biso


.3915
.2199
.7111
.6159
.5639
.6431
.6081
.6489
.7241
.7470
.8199
.8619
.9261
.8797
.3949
.1171
.4179
.5128


(15)
(10)
(10)
(10)
(13)
(11)
(12)
(13)
(11)
(11)
(11)
(12)
(12)
(3)
(3)
(4)
(10)
(12)


.4647
.3069
.5070
.3172
.3516
.2165
.1462
.0562
.0355
.1084
.0990
.0053
.2701
.7394
.2004
.0688
.0893
.3840


(7)
(5)
(6)
(6)
(6)
(6)
(6)
(6)
(6)
(6)
(5)
(6)
(5)
(2)
(1)
(2)
(5)
(6)


.6536
.4633
1.0026
.8871
.8119
.9036
.8501
.8700
.9432
.9917
1.0688
1.1040
1.2025
.1446
.6431
.3107
.1835
.2638


(5)
(4)
(4)
(4)
(4)
(4)
(4)
(5)
(4)
(4)
(4)
(5)
(4)
(1)
(1)
(1)
(4)
(4)


3.7
2.0
2.0
2.1
2.9
2.3
2.7
3.1
2.3
2.2
2.2
2.9
2.4
3.3
2.5
3.7
4.4
5.5


(4)
(3)
(3)
(3)
(4)
(3)
(4)
(4)
(3)
(3)
(3)
(3)
(3)
(2)
(2)
(2)
(3)
(4)


Biso is the Mean of the Principal
Axes of the Thermal Ellipsoid


C10
Cll
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C13
C14
C15
W3
W4














Table 3-2. Bond Distances(A) and Angles()


Fel Cll
Fel W1
Fel 01
Fel 02
Fel N3
Fel N4
Fel N5
01 Cl
02 Cll
N3 N2
N3 C2
N4 C4
N4 C8
N5 N6
N5 C9
N1 C1
N2 C1
N6 C11
N7 Cll
C2 C3
C2 C4
C4 C5
C5 C6
C6 C7
C7 C8
C8 C9
C9 C10


Cll-Fel-Wl
Cll-Fel-01
Cll-Fel-02
W1-Fel-01
W1-Fel-02
01-Fel-02
Fel-01-Cl
Fel-02-C11
N2-N3-C2


2.2644(22)
2.067(5)
2.095(5)
2.124(5)
2.218(6)
2.193(6)
2.203(6)
1.265(9)
1.260(9)
1.331(9)
1.275(10)
1.357(10)
1.342(10)
1.376(9)
1.275(10)
1.318(10)
1.359(10)
1.338(10)
1.342(10)
1.497(11)
1.467(10)
1.394(11)
1.387(13)
1.366(13)
1.392(12)
1.491(12)
1.488(11)


176.5(2)
93.2(2)
96.9(1)
88.7(2)
86.4(2)
75.7(2)
118.9(5)
118.0(5)
122.3(6)


Fe2 C12
Fe2 W2
Fe2 03
Fe2 04
Fe2 N10
Fe2 Nil
Fe2 N12
03 C12
04 C22
N10 N9
N10 C13
N11 C15
N11 C19
N12 N13
N12 C20
N8 C12
N9 C12
N13 C22
N14 C22
C13 C14
C13 C15
C15 C16
C16 C17
C17 C18
C18 C19
C19 C20
C20 C21


C8-C9-C10
02-C11-N6
02-C11-N7
N6-C11-N7
N9-N10-C13
C15-N11-C19
N13-N12-C20
N10-N9-C12
N12-N13-C22


2.5631(23)
2.174(5)
2.184(5)
2.207(5)
2.183(6)
2.195(6)
2.223(6)
1.237(9)
1.233(9)
1.378(9)
1.293(9)
1.316(10)
1.367(10)
1.374(8)
1.290(10)
1.353(10)
1.372(9)
1.368(10)
1.343(10)
1.474(11)
1.492(12)
1.411(12)
1.374(13)
1.436(12)
1.370(11)
1.470(11)
1.515(12)


119.4(7)
121.2(7)
121.8(7)
117.0(7)
119.8(6)
120.0(6)
121.7(6)
112.2(6)
113.9(6)

























Table 3-2 (cont.)


C4-N4-C8
N6-N5-C9
N3-N2-C1
N5-N6-C11
01-C1-N1
01-C1-N2
N1-C1-N2
N3-C2-C3
N3-C2-C4
C3-C2-C4
N4-C4-C2
N4-C4-C5
C2-C4-C5
C4-C5-C6
C5-C6-C7
C6-C7-C8
N4-C8-C7
N4-C8-C9
C7-C8-C9
N5-C9-C8
N5-C9-C10


120.7(6)
121.5(6)
114.1(6)
113.5(6)
121.8(7)
119.7(7)
118.5(7)
125.6(7)
113.0(7)
121.4(7)
114.7(6)
119.9(7)
125.3(7)
119.1(8)
120.3(8)
118.8(8)
121.2(7)
114.4(6)
124.5(7)
111.8(6)
128.7(8)


03-C12-N8
03-C12-N9
N8-C12-N9
N10-C13-C14
N10-C13-C15
C14-C13-C15
N11-C15-C13
N11-C15-C16
C13-C15-C16
C15-C16-C17
C16-C17-C18
C17-C18-C19
N11-C19-C18
N11-C19-C20
C18-C19-C20
N12-C20-C19
N12-C20-C21
C19-C20-C21
04-C22-N13
04-C22-N14
N13-C22-N14


122.4(7)
121.9(7)
115.7(6)
125.8(8)
111.7(6)
122.4(7)
114.9(7)
122.3(7)
122.8(7)
117.8(8)
120.3(8)
117.2(7)
122.3(7)
113.7(7)
124.0(7)
113.7(7)
123.9(7)
122.4(7)
120.4(7)
124.6(7)
115.0(7)
















48









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ttofc 00 3S 00002
cn$ m mN0 N0wv wmNm
a) C). .
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r- ) z NNL Y Y NNNcqC)"mNNNc
Q $4hh h hh h ~ h~~ h
E-4 ~ 00 o o~0 0ddoo ~ d

N VV VV VYVq CA VY VV
M v4r4 -I00W -I0N0 0Mr4















49









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o5
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0




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SIO II I I H HM














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0dd44 d ov v v T-4d d05 o
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Yi-4














* 4 04 C4 ,* ,* ; C4 C4 1 ,* N, N I ko
0*








C
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C4 '- 4 IM
mNC a
am -


00uuuuuuuuuuuuuuuuuuuuuuu














Table 3-4. Ligand Hydrogen Atomic Parameters x,y,z and Biso.


x y z Biso


H1(N1) -.0083 .4996 .1851 3.2
H2(N1) -.1751 .5412 .2113 3.2
H3(N2) .0110 .6694 .2611 3.2
H4(C3) -.2010 .3353 .6303 3.2
H5(C3) .0088 .8044 .3246 3.2
H6(C3) -.0264 .3303 .5968 3.2
H7C5) -.2386 .3430 .5094 3.2
H8(C6) .3402 .8195 .6205 3.2
H9(C7) .3718 .6529 .6609 3.2
H10(C10) .4297 .4216 .6529 3.2
H11(C1O) -.4994 .4879 .6650 3.2
H12(C10) .3151 .4682 .6813 3.2
H13(N6) .3193 .3126 .5743 3.2
H14(N7) -.2609 .6866 .4966 3.2
H15(N7) .1658 .1744 .4155 3.2
H16(N8) .3187 .1321 .0417 3.2
H17(N8) -.2080 .6298 .0443 3.2
H18(N9) -.3888 .4878 .8936 3.2
H19(C14) -.5506 .8003 .2380 3.2
H20(C14) -.4743 .8987 .1867 3.2
H21(C14) -.6696 .8921 .2106 3.2
H22(C16) -.5474 .6594 .2028 3.2
H23(C17) .3863 .5015 .1719 3.2
H24(C18) .2388 .4654 .0406 3.2
H25(C21) .0196 .4956 .8776 3.2
H26(C21) .0854 .4712 .9317 3.2
H27(C21) .1906 .4981 .8433 3.2
H28(N13) .0572 .6371 .7953 3.2
H29(N14) -.0879 .7769 .7410 3.2
H30(N14) .0807 .7722 .7251 3.2


Biso is the Mean of the Principal
Axes of the Thermal Ellipsoid












51
Third, the existence of an OH" ion in this water soluble

compound would imply that it should act as a strong base in

aqueous solution. Aqueous solutions of this compound were

found to be acidic and not at all basic. Finally, though

there is evidence of hydrogen bonding, most notably between

N6-H(N6)*-C1l4, N2-H(N2)** C13, N13-H(N13) C15 with

distances between the hydrogen and chloride of 2.10(4),

2.48(4) and 2.45(4)A respectively, there is no evidence of

strong hydrogen bonding involving either of the uncoordinated

water molecules as might be expected if one were in fact a OH"

ion.

Additional evidence for an Fe(II)/Fe(III) assignment

comes from a comparison of bond lengths within the immediate

coordination sphere of each Fe-cation. Table 3-5 shows that

Fel has much shorter bond lengths within the coordination

sphere than does Fe2. Since first row transition metals tend

generally to be ionic in nature, it is reasonable to expect

that shorter bond lengths would be observed for a 3+ cation as

opposed to a cation carrying a 2+ charge. Thus our

observations suggest that the Fel-cation is 3+ and the Fe2-

cation is 2+. Furthermore, comparing the coordination sphere

bond lengths of the two complexes in this compound with the

previously reported Fe(II) and Fe(III) complexes as is shown

in Table 2-5, reveals that the bond lengths of Fe2 parallel
















Table 3-5. Bond Lengths Observed Within the
Immediate Coordination Sphere in A.


III


Fe Cl 2.506

Fe 0 2.153



Fe 01 2.192

Fe 02 2.175

Fe N3 2.195

Fe N4 2.229

Fe N5 2.229


2.563

2.174



2.207

2.184

2.183

2.195

2.223


2.362

2.325(C1)



2.074

2.131

2.200

2.196

2.203


I = Fe(DAPSC)II,

II = Fe2 complex


J. Am. Chem. Soc., (1975),16,6505.

discussed in this chapter.


III = Fe(DAPSC)III, Inorq. Chem., (1976), 15, 1814.

IV = Fel complex discussed in this chapter.


2.261

2.067



2.095

2.124

2.218

2.183

2.203


Where












53

those observed for the Fe(II) complex and a similar situation

exists between Fel and the Fe(III) complex.

Due to the unique nature of this compound, we have now

begun a theoretical investigation exploring the electronic and

conformational characteristics of the associated molecules by

preforming semi-empirical geometry optimization calculations.

The details of this work will be presented in chapter 6.
















CHAPTER 4

PENTAGONAL BIPYRAMIDAL COMPLEXES OF Cr(III)
WHICH DISPLAY A STATIC JAHN-TELLER DISTORTION


Introduction


Pentagonal-bipyramidal complexes of Cr(III) are extremely

rare and to date only four reports[9,9,29,30] of such compounds

have appeared in the literature. In each instance a planar

pentadentate ligand was employed to obtain this unique

geometry around the chromium-cation. An intriguing aspect of

these complexes is the pronounced asymmetry observed in the

equatorial plane of the pentagonal bipyramid. In two of the

reports[9,29] this dramatic asymmetry has been attributed to

two effects: a static Jahn-Teller[31] distortion arising from

orbital degeneracy and the stronger attraction of a negatively

charged section of the ligand to the metal cation.

Utilizing both DAPSC and DAPBAH, two new complexes of

Cr(III) displaying PBP geometry have been prepared. The

reaction of DAPSC with Cr2O 2- in a reducing medium produced a

Cr(III) cation [Cr(DAPSC)(H20)2]2*, a product previously

isolated[9] but not structurally characterized. Combining

DAPBAH with a solution of Cr2' in 0.6M HC1 produced the cation

[Cr(DAPBAH) (H20)2]2.












55

The synthesis and characterization of both PBP-Cr(III)

complexes by X-ray diffraction techniques is presented in this

chapter. In addition, it is shown by means of a group

theoretical treatment that a static Jahn-Teller31 distortion

is indeed possible for a Cr(III) cation in a PBP-field.



Experimental

Materials. The 2,6-Diacetylpyridine purchased from

Aldrich, semicarbazide hydrochloride purchased from Eastman

Chemicals, and the benzoic acid hydrazide purchased from

Pfaltz and Bauer were used as supplied. All other solvents

and chemicals were reagent grade.

Preparation of [Cr(DAPSC)(H20),12( NOj2 12 H0,, (I). KCr20,

(0.0735g, 0.2 mmole) was added to 45 mL H20 having a pH = 1.00

(conc. HNO3). DAPSC (0.390g, 1.4 mmole), prepared by the

method previously described[9], was then added to this

solution. The resulting slurry was stirred and heated to 57'

C for 1 hr. The green solution was then filtered through a

fine glass frit and cooled to room temp (23' C). At this

point pH = 3.30. Slow evaporation of the filtrate gave a crop

of brown plates after 23 days.

Preparation of rCr(DAPBAH)(H,20)12+C1, 4H,O, (II).

Chromium metal (0.0265g, 0.5 mmole) was placed into 30 mL of

a 0.06 M HC1 solution (under N2) to produce a 0.017 M Cr2*

solution. DAPBAH (0.2003g, 0.5 mmole), prepared by the method












56

previously described[15], was then added to this solution.

Upon the addition of DAPBAH, the blue Cr2* solution rapidly

turned to a yellow/green color. Stirring was continued for 1

hr. after which the N2 atmosphere was removed and the solution

filtered. The filtrate had a pH = 0.90 and no further color

changes were observed. Green cubic shaped crystals were

obtained in good yield within 24 hrs..

Magnetic Measurements. The magnetic moments of both

compounds were determined in a 2% tert-butyl alcohol-water

solution by NMR techniques[32]. The average of three

measurements for I and II was 4.03 0.04 and 4.07 0.04

respectively.

Data Collection and Structure Refinement. Crystals

suitable for diffraction studies were mounted on the end of a

glass fiber and all subsequent measurements were made using a

Nicolet R3m diffractometer with graphite-monochromated Mo-Ka

radiation (k = 0.71069A). The unit cell dimensions were

determined by a least squares refinement of 25 automatically

centered reflections. A variable-speed (1* 29.3*) 20 scan

technique was used to measure the intensity data from 0 to

50* and 40 in 20 for the complexes I, and II respectively.

Two standard reflections were measured every 98 reflections to

monitor for any decomposition during the X-ray analysis. No

absorption corrections were made. The pertinent crystal data

is given in Table 4-1.












57

The data reduction, structure solution and final

refinement were performed using the NRCVAX (PC-Version)[18]

package of programs. All non-hydrogen atoms were located by

the heavy-atom method (Patterson and Fourier syntheses) and

refined anisotropically by full-matrix least squares. The

hydrogen atoms were located by the calculation of a difference

Fourier map and refined isotropically for complex I. For

complex II, H-atoms were placed at calculated positions and

not refined. The final positional parameters are given in

Tables 4-2 and 4-3 with the final bond distances involving the

non-hydrogen atoms and bond angles listed in Tables 4-4 and 4-

5 respectively. The anisotropic thermal parameters are listed

in Tables 4-6 and 4-7 and the hydrogen positional parameters

are given in Tables 4-8 and 4-9.



Results and Discussion

The crystals of I and II consist of [Cr(DAPSC)(H2O)2]2+

and [Cr(DAPBAH)(H20)2]2 cations respectively and display PBP

geometry which is easily seen in Figures 4-1 and 4-2. The

bond lengths observed within each of the coordination spheres

are presented in Table 4-10. It is clear from the bond

lengths in Table 4-10 that the five bonds in each of the

equatorial planes differ significantly from each other.

Consequently there is notable distortion of the respective

pentagonal bipyramid in each case.














Table 4-1. Crystal Data for I and II


I II


Crystal System
Space Group
a, A
b, A
c, A
a, 0
P,
Y,
Vol., A3
mol. wt.
Z
d(calcd), g/cm3
Crystal Size, mm3


p, cm-'
Data with I > 2.5 oI
R", %
Rwb, %


Monoclinic
P21/n
11.726
14.730
11.856
90
105.52
90
1973
508.34
4
1.71
0.10 x 0.12
x 0.18
11.4
2580


4.4
4.6


Triclinic
P1
14.404
14.689
15.102
62.56
75.17
74.90
2703
601.90
4
1.48
0.09 x 0.11
x 0.17
6.4
2509
7.0
8.3


R WIF Fo-2














Table 4-2. Atomic Parameters x,y,z and Biso for Compound I.
E.S.Ds. refer to the last digit printed.

x y z Biso


.08266(6)
-.0838 (3)
.2469 (3)
.0307 (2)
.0959 (3)
.1028 (3)
.0390 (3)
.0057 (3)
-.0251 (4)
.1342 (3)
.1477 (3)
.1329 (4)
.1373 (4)
.1552 (4)
.1370 (5)
.1028 (4)
.0860 (4)
.0523 (4)
.0373 (7)
.0045 (4)
.1564 (4)
.1984 (6)
.1254 (3)
.2823 (4)
.4585 (3)
.2832 (4)
.2722 (5)
.2924 (5)
.3972 (3)
.5285 (4)
.4487 (3)
.2524 (4)


.60588(4)
.6001 (3)
.6178 (2)
.5761 (2)
.4725 (1)
.7389 (2)
.7390 (2)
.7227 (2)
.6107 (3)
.5777 (3)
.4875 (2)
.3485 (2)
.7326 (3)
.8078 (3)
.8927 (3)
.8997 (3)
.8213 (3)
.8201 (3)
.9035 (4)
.6331 (3)
.6392 (4)
.6167 (4)
.4385 (3)
.6743 (4)
.6637 (2)
.7165 (3)
.7120 (4)
.5918 (4)
.7332 (2)
.6468 (3)
.6095 (2)
.9328 (3)


.23319(5)
.1449 (3)
.3282 (3)
.3865 (2)
.2355 (2)
.1458 (3)
.3300 (3)
.4287 (3)
.5502 (3)
.0854 (3)
.0616 (3)
.1398 (4)
.0469 (3)
-.0160 (4)
.0261 (4)
.1287 (4)
.1866 (4)
.2978 (4)
.3615 (6)
.4550 (3)
.0136 (4)
-.0897 (5)
.1478 (3)
.6070 (4)
.1838 (3)
.5198 (3)
.6935 (4)
.6065 (6)
.1647 (3)
.1239 (4)
.2596 (3)
.7621 (4)


Biso is the Mean of the Principal
Axes of the Thermal Ellipsoid


Cr
Wl
W2
01
02
N1
N2
N3
N4
N5
N6
N7
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
N8
N9
03
04
05
06
07
08
W3


2.04
2.7
3.1
2.4
2.5
2.3
2.5
2.8
3.4
2.2
2.4
3.1
2.5
3.3
3.8
3.4
2.5
2.5
4.1
2.4
2.5
4.0
2.3
4.5
2.6
6.7
8.9
9.7
4.2
5.6
4.0
5.8


(2)
(1)
(1)
(1)
(1)
(1)
(1)
(2)
(2)
(2)
(1)
(2)
(2)
(2)
(2)
(2)
(2)
(2)
(3)
(2)
(2)
(3)
(2)
(2)
(2)
(2)
(3)
(4)
(2)
(2)
(2)
(2)













Table 4-3. Atomic Parameters x,y,z and Biso for Compound II.
E.S.Ds. refer to the last digit printed.

x y z Biso
Crl .6354 (2) .8579 (2) .0952 (2) 2.3 (2)
Cr2 .8675 (2) .40859(2) .6351 (2) 2.2 (2)
C11 .1162 (4) .1741 (4) .7679 (4) 4.6 (3)
C12 .6169 (4) .2706 (4) .6967 (4) 4.7 (3)
C13 .9184 (4) .8115 (4) .9019 (4) 4.7 (3)
C14 .5941 (5) .6068 (4) .6941 (4) 5.7 (4)
01 .6134 (9) 1.0274 (8) .0454 (8) 3.0 (7)
02 .6350 (8) .9153 (7) -.0514 (7) 2.3 (6)
03 .8825 (8) .4664 (7) .4862 (7) 2.0 (6)
04 .8711 (9) .5648 (7) .5940 (7) 2.7 (6)
W1 .4912 (10) .8735 (8) .1230 (8) 3.9 (8)
W2 .7796 (8) .8456 (8) .0737 (8) 3.1 (6)
W3 .7203 (9) .4415 (8) .6485 (8) 3.0 (7)
W4 1.0119 (9) .3733 (7) .6264 (8) 3.3 (7)
N1 .6340 (10) .7264 (8) .2435 (8) 1.9 (7)
N2 .6292 (11) .9058 (9) .2241 (9) 2.7 (8)
N3 .6312 (10) 1.0109 (9) .1988 (8) 2.3 (8)
N4 .6435 (11) .7297 (9) .0724 (9) 2.6 (9)
N5 .6433 (11) .7472 (9) -.0273 (9) 2.6 (8)
N6 .8629 (9) .2720 (9) .7853 (9) 1.8 (7)
N7 .8652 (10) .2848 (10) .6139 (8) 2.5 (8)
N8 .8632 (11) .3040 (9) .5153 (9) 2.8 (8)
N9 .8599 (11) .4476 (9) .7776 (9) 2.8 (9)
N10 .8654 (11) .5488 (9) .7531 (9) 2.9 (9)
Cl .6303 (13) .7348 (11) .3296 (11) 2.3 ( 9)
C2 .6229 (14) .6470 (13) .4216 (11) 3.0 (11)
C3 .6216 (15) .5539 (12) .4244 (12) 3.3 (11)
C4 .6247 (15) .5470 (12) .3363 (12) 3.3 (12)
C5 .6311 (14) .6358 (11) .2452 (13) 3.4 (10)
C6 .6299 (12) .8388 (11) .3204 (10) 1.8 (9)
C7 .6231 (15) .8644 (15) .4059 (12) 4.0 (12)
C8 .6203 (12) 1.0673 (12) .1024 (11) 2.2 (9)
C9 .6361 (14) .6364 (11) .1468 (12) 3.1 (10)
C10 .6302 (15) .5453 (13) .1304 (13) 3.7 (12)
C11 .6391 (14) .8479 (13) -.0851 (12) 3.1 (11)
C12 .8624 (11) .1812 (11) .7821 (10) 1.5 (8)
C13 .8640 (14) .0851 (12) .8725 (12) 3.1 (10)
C14 .8717 (14) .0865 (12) .9604 (11) 3.1 (10)
C15 .8755 (15) .1805 (12) .9643 (12) 3.3 (11)
C16 .8703 (13) .2735 (12) .8719 (11) 2.6 (9)
C17 .8654 (13) .1881 (11) .6832 (11) 2.7 (10)
C18 .8680 (17) .0982 (13) .6622 (14) 4.6 (13)
C19 .8783 (13) .4002 (12) .4537 (11) 2.6 (10)

















Table 4-3 (cont).


x y z Biso


.8665 (15)
.8692 (15)
.8659 (13)
.6147 (14)
.6275 (16)
.6220 (16)
.5971 (15)
.5821 (17)
.5924 (14)
.6360 (13)
.6325 (13)
.6276 (15)
.6258 (16)
.6308 (16)
.6419 (16)
.8835 (16)
.8739 (16)
.8822 (13)
.9034 (14)
.9045 (18)
.8945 (16)
.8737 (14)
.8844 (15)
.8936 (16)
.8858 (16)
.8714 (16)
.8621 (15)
.8245 (10)
.7073 (13)
.3229 (15)
.6014 (19)
.9021 (13)


.3758
.3870
.6071
1.1835
1.2414
1.3472
1.3977
1.3399
1.2321
.8831
.8182
.8546
.9603
1.0250
.9872
.4349
.5408
.5687
.4942
.3925
.3589
.7203
.7674
.8725
.9291
.8829
.7789
.6335
1.0800
.7132
.2406
.0596


(12)
(13)
(12)
(11)
(12)
(13)
(13)
(14)
(12)
(11)
(13)
(13)
(14)
(14)
(12)
(12)
(13)
(13)
(12)
(15)
(14)
(12)
(12)
(14)
(12)
(13)
(13)
(8)
(10)
(11)
(16)
(11)


.8682
.9612
.6497
.0572
-.0454
-.0854
-.0214
.0846
.1233
-.1924
-.2337
-.3339
-.3950
-.3577
-.2565
.3427
.2745
.1718
.1359
.2028
.3076
.6099
.6638
.6167
.5149
.4629
.5056
.9051
.3062
.5256
.3560
.2059


(12)
(13)
(11)
(12)
(12)
(12)
(14)
(13)
(12)
(11)
(12)
(13)
(13)
(13)
(11)
(12)
(12)
(12)
(12)
(16)
(13)
(12)
(13)
(14)
(14)
(14)
(12)
(8)
(10)
(10)
(17)
(11)


3.5 (11)
3.7 (12)
2.4 (10)
2.9 (11)
3.8 (12)
4.1 (12)
4.0 (12)
4.5 (13)
3.0 (10)
2.2 (10)
2.7 (10)
3.9 (13)
4.3 (13)
4.3 (13)
3.8 (12)
3.8 (12)
4.0 (12)
3.2 (10)
3.3 (11)
5.5 (15)
4.6 (13)
3.1 (11)
3.7 (12)
4.5 (13)
4.5 (12)
4.0 (12)
3.6 (12)
4.1 (8)
6.7 (11)
7.7 (12)
12.4 (19)
7.3 (11)


Biso is the Mean of the Principal
Axes of the Thermal Ellipsoid


C20
C21
C22
C81
C82
C83
C84
C85
C86
C111
C112
C113
C114
C115
C116
C191
C192
C193
C194
C195
C196
C221
C222
C223
C224
C225
C226
W5
W6
W7
W8
W9














Table 4-4. Bond Lengths (A) and Bond Angles (*) for I.


1.955(4)
1.962(3)
2.112(2)
1.970(3)
2.258(3)
2.396(3)
2.043(4)
1.261(5)
1.282(4)
1.342(5)
1.340(5)
1.350(5)
1.276(5)
1.357(5)
1.309(5)
1.376(5)
1.333(5)


C11
C2
C9
C3
C4
C5
C6
C7
C10
03
04
05
06
07
08
C9


1.333(5)
1.382(6)
1.465(6)
1.385(7)
1.383(6)
1.385(6)
1.474(6)
1.478(7)
1.475(7)
1.209(6)
1.199(6)
1.221(8)
1.237(5)
1.246(5)
1.229(4)
1.316(7)


W1-Cr-W2
W1-Cr-01
W1-Cr-02
W1-Cr-N5
W2-Cr-01
W2-Cr-02
W2-Cr-N5
01-Cr-02
01-Cr-N5
02-Cr-N5
Cr-01-C8
Cr-02-Cll
C1-N1-C5
N3-N2-C6
N2-N3-C8
Cr-N5-N6
Cr-N5-C9
N6-N5-C9
N5-N6-Cll
N1-C1-C2
N1-C1-C9
C2-C1-C9
C1-C2-C3


176.3(2)
88.6(1)
91.6(1)
90.8(2)
89.4(1)
91.1(1)
92.3(2)
79.7(1)
156.3(1)
76.6(1)
126.3(2)
114.6(2)
119.1(3)
120.8(3)
113.3(3)
116.7(3)
124.8(3)
118.6(4)
108.0(3)
122.7(4)
113.8(3)
123.4(4)
118.0(4)


C2-C3-C4
C3-C4-C5
N1-C5-C4
N1-C5-C6
C4-C5-C6
N2-C6-C5
N2-C6-C7
C5-C6-C7
01-C8-N3
01-C8-N4
N3-C8-N4
N5-C9-C1
N5-C9-C10
C1-C9-C10
02-C11-N6
02-C11-N7
N6-C11-N7
03-N8-04
03-N8-05
04-N8-05
06-N9-07
06-N9-08
07-N9-08


119.5(4)
119.1(4)
121.5(4)
114.4(3)
124.1(4)
111.2(3)
125.8(4)
122.9(4)
118.7(3)
123.6(4)
117.7(4)
113.6(4)
123.4(5)
122.9(5)
124.1(3)
119.0(4)
117.0(3)
121.2(6)
119.0(5)
119.8(6)
120.0(4)
120.5(3)
119.5(4)


W1
W2
01
02
N1
N2
N5
C8
C11
C1
C5
N3
C6
C8
C8
N6
C11















Bond Lengths (A) and Angles () for II.


Crl
Crl
Crl
Crl
Crl
Crl
Crl
Cr2
Cr2
Cr2
Cr2
Cr2
Cr2
Cr2
01
02
03
04
N1
N1 -
N2
N2
N3
N4-
N4 -
N5 -
N6 -
N6
N7-
N7
N8
N9 -
N9-
N10
Cl -
C1 -
C2 -
C3 -
C4 -


- 01
- 02
- W1
- W2
- N1
- N2
- N4
- 03
-04
- W3
- W4
- N6
-N7
-N9
- C8
SC11
SC19
C22
SCl
SC5
N3
SC6
C8
N5
C9
SC11
C12
C16
N8
SC17
C19
N10
C20
- C22
C2
C6
C3
C4
C5


2.203(10)
1.974(9)
1.984(14)
1.992(12)
2.181(11)
2.330(13)
2.034(11)
1.978(9)
2.094(10)
2.027(12)
1.993(13)
2.231(12)
1.996(13)
2.440(13)
1.278(18)
1.290(18)
1.294(18)
1.236(17)
1.349(19)
1.331(20)
1.415(16)
1.330(18)
1.330(19)
1.408(17)
1.322(19)
1.320(20)
1.359(18)
1.350(20)
1.389(17)
1.320(19)
1.325(20)
1.376(16)
1.296(20)
1.392(19)
1.396(21)
1.468(21)
1.354(23)
1.369(23)
1.395(22)


C5 -
C6 -
C8 -
C9 -
C11
C12
012
C13
C14
C15
C16
C17
C19
C20
C22
C81
C81
C82
C83
C84
C85
C111
C111
C112
C113
C114
C115
C191
C191
C192
C193
C194
C195
C221
C221
C222
C223
C224
C225


01-Crl-02
01-Crl-Wl
01-Crl-W2
01-Crl-N1
01-Crl-N4


76.1(4)
85.9(4)
92.4(4)
133.1(4)
152.5(5)


C1-C6-C7
01-C8-N3
01-C8-C81
N3-C8-C81
N4-C9-C5


125.0(13)
122.8(14)
117.7(13)
119.5(13)
111.5(13)


C9
C7
C81
C10
- C111

- C13
- C17
- C14
- C15

-C20
- C18
- C191
- C21
- C221
- C82
- C86
- C83
- C84
- C85
- C86
- C112
- C116
- C113
- C114
- C115
- C116
- C192
- C196
- C193
- C194
- 0195
- C196
- C222
- C226
- C223
- C224
- C225
- C226


1.465(24)
1.477(22)
1.505(21)
1.495(23)
1.466(22)
1.442(20)
1.439(21)
1.370(24)
1.424(23)
1.436(21)
1.465(22)
1.484(23)
1.498(21)
1.498(24)
1.509(21)
1.371(22)
1.408(22)
1.371(23)
1.40(3)
1.41(3)
1.392(23)
1.375(21)
1.394(21)
1.369(23)
1.390(25)
1.33(3)
1.403(24)
1.409(23)
1.399(25)
1.391(23)
1.368(24)
1.36(3)
1.40(3)
1.342(24)
1.435(23)
1.398(23)
1.39(3)
1.33(3)
1.387(23)


Table 4-5.














Table 4-5 (cont.).


02-Crl-Wl
02-Crl-W2
02-Crl-Nl
02-Crl-N4
W1-Crl-W2
W1-Crl-Nl
W1-Crl-N4
W2-Crl-Nl
W2-Crl-N4
N1-Crl-N4
03-Cr2-04
03-Cr2-W3
03-Cr2-W4
03-Cr2-N6
03-Cr2-N7
04-Cr2-W3
04-Cr2-W4
04-Cr2-N6
04-Cr2-N7
W3-Cr2-W4
W3-Cr2-N6
W3-Cr2-N7
W4-Cr2-N6
W4-Cr2-N7
N6-Cr2-N7
Crl-01-C8
Crl-02-C11
Cr2-03-C19
Cr2-04-C22
Crl-Nl-Cl
Crl-N1-C5
C1-N1-C5
N3-N2-C6
N2-N3-C8
Crl-N4-N5
Crl-N4-C9
N5-N4-C9
N4-N5-C11
Cr2-N6-C12
Cr2-N6-C16
C12-N6-C16
Cr2-N7-N8
Cr2-N7-C17
N8-N7-C17
N7-N8-C19
N10-N9-C20


91.1(5)
91.5(5)
150.3(4)
76.7(5)
176.4(5)
86.7(5)
90.0(5)
92.2(5)
93.0(5)
73.7(5)
78.7(4)
91.9(4)
89.8(4)
149.9(4)
78.0(4)
89.6(4)
91.2(4)
131.1(4)
156.6(4)
178.2(4)
92.4(4)
89.2(5)
85.9(4)
90.7(5)
72.3(4)
122.0(10)
115.2(9)
113.5(9)
128.2(9)
123.7(9)
115.2(10)
120.9(12)
117.2(12)
108.5(12)
116.3(8)
123.4(10)
119.8(12)
108.2(11)
114.2(9)
124.7(9)
120.8(12)
115.6(9)
126.9(10)
117.6(12)
109.6(12)
120.8(12)


N4-C9-C10
C5-C9-C10
02-C11-N5
02-C11-C111
N5-C11-C111
N6-C12-C13
N6-C12-C17
C13-C12-C17
C12-C13-C14
C13-C14-C15
C14-C15-C16
N6-C16-C15
N6-C16-C20
C15-C16-C20
N7-C17-C12
N7-C17-C18
C12-C17-C18
03-C19-N8
03-C19-C191
N8-C19-C191
N9-C20-C16
N9-C20-C21
C16-C20-C21
04-C22-N10
04-C22-C221
N10-C22-C221
C8-C81-C82
C8-C81-C86
C82-C81-C86
C81-C82-C83
C82-C83-C84
C83-C84-C85
C84-C85-C86
C81-C86-C85
C11-C111-C112
C11-C111-C116
C112-C111-C116
C111-C112-C113
C112-C113-C114
C113-C114-C115
C114-C115-C116
C111-C116-C115
C19-C191-C192
C19-C191-C196
C192-C191-C196
C191-C192-C193


123.1(15)
125.4(13)
123.5(14)
119.4(14)
117.0(13)
120.7(13)
115.4(12)
123.8(14)
118.5(14)
121.4(14)
116.8(14)
121.7(13)
116.5(13)
121.7(14)
111.2(13)
124.4(14)
124.3(13)
122.6(13)
119.3(14)
117.9(14)
110.3(14)
128.8(14)
120.9(14)
120.8(13)
122.9(13)
115.8(12)
121.3(14)
118.2(13)
120.4(14)
120.7(15)
119.9(15)
120.4(15)
118.5(15)
120.0(14)
123.6(14)
117.8(13)
118.5(14)
121.8(15)
118.6(15)
121.1(16)
120.6(16)
118.9(15)
121.9(14)
118.2(14)
119.9(15)
119.6(15)































Table 4-5 (cont.).


N9-N10-C22
N1-C1-C2
N1-C1-C6
C2-C1-C6
C1-C2-C3
C2-C3-C4
C3-C4-C5
N1-C5-C4
N1-C5-C9
C4-C5-C9
N2-C6-C1
N2-C6-C7


109.0(11)
119.3(14)
116.9(12
123.8(14)
120.5(15)
119.4(14)
119.2(14)
120.7(15)
115.8(13)
123.5(14)
108.3(12)
126.5(13)


C192-C193-C194
C193-C194-C195
C194-C195-C196
C191-C196-C195
C22-C221-C222
C22-C221-C226
C222-C221-C226
C221-C222-C223
C222-C223-C224
C223-C224-C225
C224-C225-C226
C221-C226-C225


120.6(15)
119.2(16)
122.8(17)
117.2(16)
126.2(14)
113.0(14)
120.7(15)
120.3(16)
119.2(17)
120.1(15)
123.1(17)
116.3(16)




























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Table 4-8. Hydrogen Atomic Parameters x,y,z and Biso for I.
E.S.Ds. refer to the last digit printed.

x y z Biso


H1(N4)
H2(N4)
H3(N3)
H4(C7)
H5(C7)
H6(C7)
H7(C4)
H8(C3)
H9(C2)
H10(C10)
H12(C10)
H13(C10)
H14(N7)
H15(N7)
H16(W1)
H17(W1)
H18(W2)
H19(W2)
H20(W3)
H21(W3)


-.029(4)
-.048(4)
.006(4)
-.023(5)
.108(6)
.030(6)
.092(4)
.150(4)
.182(4)
.252(5)
.247(5)
.146(5)
.153(4)
.127(3)
-.103(5)
-.126(5)
.301(4)
.262(6)
.266(7)
.183(7)


.559(3)
.648(3)
.755(3)
.904(4)
.913(5)
.943(4)
.955(3)
.945(4)
.802(3)
.570(4)
.661(4)
.605(4)
.327(3)
.316(3)
.574(4)
.598(4)
.623(3)
.634(5)
.846(6)
.930(5)


.566(4)
.582(4)
.478(4)
.399(5)
.426(6)
.328(6)
.154(4)
-.017(4)
-.080(4)
-.074(4)
-.109(5)
-.143(5)
.085(4)
.188(4)
.088(5)
.173(5)
.304(4)
.389(6)
.755(7)
.726(6)


3.6(12)
2.2(10)
3.8(11)
9.0(16)
8.8(21)
7.4(19)
3.8(11)
4.8(12)
3.3(10)
5.6(14)
6.0(15)
5.4(18)
3.5(10)
1.8(19)
5.8(19)
3.3(16)
3.9(13)
6.8(21)
15.2(22)
10.9(23)














Table 4-9. Hydrogen Atomic Parameters x,y,z and Biso for II.
E.S.Ds. refer to the last digit printed.

x y z Biso

H1(C7) .690 .855 .394 3.9
H2(C7) .659 .805 .462 3.9
H3(C7) .560 .847 .453 3.9
H4(C2) .618 .654 .491 3.6
H5(C3) .619 .485 .495 3.6
H6(C4) .622 .473 .338 4.3
H7(C10) .572 .502 .198 3.9
H8(C10) .699 .511 .160 3.9
H9(C10) .608 .529 .081 3.9
H10(C18) .944 .062 .658 6.0
Hl1(C18) .835 .128 .607 3.9
H12(C18) .817 .067 .704 3.9
H13(C13) .859 .014 .871 3.8
H14(C14) .875 .015 1.029 3.6
H15(C15) .881 .183 1.033 4.5
H16(C21) .875 .460 .946 3.9
H17(C21) .806 .372 1.009 3.9
H18(C21) .933 .331 .989 4.6
H19(C112) .635 .736 -.185 3.7
H20(C113) .624 .803 -.365 4.6
H21(C114) .622 .990 -.474 5.0
H22(C115) .624 1.108 -.406 5.2
H23(C116) .662 1.035 -.230 4.0
H24(C222) .884 .723 .744 4.6
H25(C223) .907 .908 .660 5.2
H26(C224) .891 1.011 .477 4.7
H27(C225) .869 .928 .383 5.1
H28(C226) .845 .745 .463 4.6
H29(C82) .642 1.204 -.095 4.6
H30(C83) .637 1.392 -.166 4.4
H31(C84) .590 1.481 -.053 4.6
H32(C85) .562 1.379 .134 5.8
H33(C86) .583 1.186 .204 3.9
H34(C192) .855 .601 .302 4.2
H35(C193) .873 .650 .120 3.6
H36(C194) .921 .516 .056 4.1
H37(C195) .915 .336 .173 6.7
H38(C196) .894 .278 .359 4.9
H39(W1) .458 .914 .062 3.9
H40(W1) .507 .900 .164 3.9
H41(W2) .806 .885 .084 3.9
H42(W2) .834 .819 .056 3.9
H43(W3) .668 .477 .676 3.9






























Table 4-9 (cont.).


x y z Biso

H44(W3) .769 .416 .682 3.9
H45(W4) 1.049 .442 .597 3.9
H46(W4) 1.078 .383 .577 3.9
H47(W5) .780 .669 .915 3.9
H48(W5) .859 .674 .887 3.9
H49(W6) .679 1.043 .259 3.9
H50(W6) .705 1.105 .264 3.9
H51(W7) .336 .718 .467 3.9
H52(W8) .633 .282 .314 3.9
H53(W8) .582 .198 .388 3.9
H54(W9) .947 .093 .195 3.9
H55(W9) .920 -.005 .198 3.9




































































Figure 4-1.


An ORTEP representation of Compound I.


























C84


C114

C115


C10


Figure 4-2. An ORTEP representation of compound II.


























Table 4-10. Bond Distances in A Within the
Coordination Sphere


I II





Cr W1 = 1.955 1.984 2.027

W2 = 1.962 1.992 1.993

01 = 2.112 2.203 1.987

02 = 1.970 1.974 2.094

N1 = 2.258 2.181 2.231

N2 = 2.396 2.330 1.996

N5 = 2.043 2.034 2.440












77

Jahn Teller Effect. Previously it was suggested[8]

that the asymmetry observed in PBP Cr(III) complexes was due

to a Jahn-Teller distortion[31] which occurs to remove the

orbital degeneracy. Since both compounds exhibit solution

magnetic moments corresponding to 3 unpaired electrons, the

central Cr ion can be described as a d3 system. The energy

level diagrams, Figure 4-3, for the d-orbitals in PBP

geometry[33,34] require placing one electron in either the

antibonding dx2_y2 or dxy orbital. Assuming regular D5h

geometry, the imposed crystal field would lead to an orbital

degeneracy which may be removable by a Jahn-Teller vibronic

distortion.

With three unpaired electrons, an electron configuration

of e" 2, e'2 is obtained for Cr(III) in a PBP field. Upon

coupling the two e", electrons, a triplet spin function is

obtained which is symmetric, consequently the antisymmetric

direct product of the two electrons must be taken as required

by the Pauli principal to produce an overall spin function

which is antisymmetric.



[e", X e"1]lnt = 3A'2



Now coupling in the e'2 electron and taking the symmetric

direct product the ground state term symbol





















01


,-r-
(a


01


Co




I


(0









14
mH
0a)






C
4a)


(CO


S0
4-a

aC
10
i- *
(0
r>
en4 -


1-4
a)


01


0)









79

[A'2 X e' 2] m = E'2



is obtained. Attention must now be given to how the spin

portion of the wave function transforms in the point group

symmetry by looking at the spin-orbit coupling effects. If

there is strong spin-orbit coupling, four states arise as

shown below but all are Kramers doublets and thus not Jahn-

Teller active.

Spin = 3/2

(i.e. quartet ground state)

3/2 = E,/2 + E3/2

[E1/2 + E3/2] X E' = E3/2 + E5/2 + E1/2 + E3/2

In the case of Cr(III) the spin-orbit coupling can be

considered weak[35]. In consequence upon taking the symmetric

direct product of the E'2 vibronic state only



[E', X E'2] = A'1 + E'



is obtained.

Although the A'l state is totally symmetric and not Jahn-

Teller active, the E', state is a two fold degenerate

vibration and could indeed give rise to a Jahn-Teller

vibronic distortion.

Although it is not our purpose to make any quantitative

calculation on the magnitude of this distortion, the Jahn-

Teller effect for a d3 metal ion in a PBP field is important









80

since the orbital degeneracy involves an electron in either a

dx2_y2 or a dxy orbital both of which participate strongly in

bonding in the equatorial plane.

Deprotonation of the Ligand. A second contribution to

the observed distortion in both PBP Cr(III) complexes arises

from the formation of a half-conjugated monoanion which

results from the deprotonation of one of the NH functions of

the respective ligand "arm" as shown in Figure 4-4. In

complex I the hydrogen atom on N6 was not located;

consequently, the ligand becomes a half-conjugated monoanion

and as a result the overall charge on the complex has a 2+

which is balanced by two N03O ions. Behavior of this type is

not unusual as has been pointed out previously[29,36,37]. The

bond lengths from the deprotonated arm to the Cr(III) ion are

shorter than those on the opposite side as might be expected

from electrostatic arguments.

The quality of the final difference map for complex I was

not of sufficient quality to locate all hydrogens with

certainty. It is likely that both molecules have lost one

proton since each molecule has two chloride ions associated

with it and requires a third negative charge to balance the 3+

state of the metal. Since the complex was obtained from a

highly acidic solution, the existence of a OH- ion rather than

a water molecule in the unit cell is unlikely.

Deprotonation of either DAPSC or DAPBAH leads to the

delocalization of the n-electrons in the ligand arm.





























1 4
No



HN O


NH2


Figure 4-4. A representation of the half-conjugated monoanion
which results from the deprotonation of the ligand.









82

Lengthening of the C=O and N=C bonds and a shortening of the

N-C bond is observed in both 1 and 2 as would be expected.

The N-N bond would also be expected to shorten though we find

the bond actually lengthens which is in accord with previous

reports[9,29]. This lengthening may be due to the presence of

a n-nodal plane perpendicular to the equatorial plane of the

pentagonal bipyramid which bisects the N-N bond. Deprotonation

of the ligand puts an additional electron into the delocalized

n-orbital which would in turn cause greater repulsion at the

nodal plane. Hence n-orbital antibonding interactions are a

more likely cause of this anomaly than ring stress in the five

membered ring resulting from the strong attraction of the

negatively charged portion of the ligand to the metal as has

been suggested[29].

In conclusion, we see that PBP complexes of Cr(III) with

either DAPSC or DAPBAH are readily obtained from aqueous

media. Moreover, these two complexes provide additional

examples of static Jahn-Teller distortions in PBP complexes.

Furthermore, the distortions observed cannot be accounted for

totally in terms of either a Jahn-Teller distortion or the

formation of a half-conjugated monoanion but rather by a

combination of both effects.















CHAPTER 5

SYNTHESIS AND CRYSTAL STRUCTURE OF A WATER SOLUBLE CATIONIC
(13,13'-CioHs6)Ru(IV) COMPLEX: CHLORO[(1-3-q:6-8-v )-2,7-
DIMETHYLOCTADIENEDIYL]SEMICARBAZIDE RUTHENIUM(IV) CHLORIDE
DIHYDRATE.


Introduction

There is current interest in high formal oxidation state

Ru complexes as models for the heme protein system, as well as

for their relevance in catalytic processes[38-43] and for

their use as oxidizing agents for organic synthesis[44].

Although stable bis(n-allyl)ruthenium complexes have been

prepared[41], the reactions of the chloro-bridged dimer di-u-

chloro-bis[(2,7,-dimethyl-octa-2,6-diene-1,8-

diyl)ruthenium(IV)] chloride,I, has not been extensively

studied. We chose to study the reaction of DAPSC with 1[45-

47] in an attempt to prepare a PBP Ru(IV) complex.

One problem encountered in preparing PBP complexes of the

second and third transition series is that the spin-orbit

coupling effect has a major influence on the splitting of the

d-orbitals. This effect magnifies the energy differences

between the d-orbitals which are initially produced by the PBP

ligand field encountered by the metal-cation. The greatest

difference in energy for second and third row metals comes

between the e'2 and e"I orbitals (Figure 4-3) with the e'2









84

orbitals increasing dramatically in energy as compared to the

e", orbitals. Thus, it is reasonable to expect that metal

cations with electron configurations of d4 or lower[4] would

be easier to isolate since it would not require the placement

of one or more electrons into the higher energy orbitals.

Since a Ru(IV) complex had been reported[48] where

bidentate ligands had been used to achieve PBP geometry, we

were interested in exploring whether a pentadentate ligand

could also be used to isolate Ru in a high formal oxidation

state. The reported oxidation state of I suggested that the

metal was d4. Furthermore, this compound was known to be air

stable and relatively uncomplicated to prepare. Consequently

we decided to use I as a source of Ru(IV) in our study.

Rather than the expected PBP complex, a novel 5-coordinate

species was isolated with an unusual trigonal bipyramidal,

TBP, geometry around the Ru center resulting from a disruption

of the chlorine bridges in the dimeric Ru starting material

and the solvolysis of the DAPSC ligand. The new complex is

the first example of a Ru(IV) ion chelated by both two (q3-

allyl) functions and a semicarbazide ligand.

Recently, the isomerism and solution equilibria for the

chloro-bridged dimer, I, was reported and the possible

existence of cationic species was postulated[49]. Indeed,

this is the first report of the isolation and structural

characterization of such a species.









85

Experimental
Materials. All solvents and chemicals were reagent grade

and were used as supplied.

Synthesis. Dichloro(2,7-dimethyl-octa-2,6-diene-l,8-

diyl)ruthenium chloride, I,[50] and DAPSC[9] were synthesized

by methods previously described. Into 35 mL of deionized H20,

DAPSC (0.045g, 0.2 mmole) was slurried together with I

(0.050g, 0.1 mmole). This mixture was stirred and heated to

55*C for two hours. A clear yellow/brown solution was

obtained which was filtered through a fine glass frit while

warm. Upon reaching room temperature (230C), the pH of the

solution was adjusted to 1.45 with HC1. Brown, air stable

single crystals were obtained from the above solution in 10

days by the slow evaporation of the solvent. The compound was

found to be quite soluble in H20 and decomposed at 1800C.

The yield of this compound can be increased dramatically

by the reaction of I with semicarbazide directly. For

example, 0.050g (0.1 mmole) of I was combined with 0.0181g

(0.2 mmole) semicarbazide hydrochloride in 35 mL deionized

water (pH = 1.50) and heated to 55C for 2 hrs.. A clear

yellow-brown solution formed which was filtered and allowed to

cool to room temperature(25 C). Slow evaporation of this

solution produced, after 12 days, brown crystals of the title

complex (yield 77%). Elemental analysis: Calc. C = 31.50%, H

= 6.01%, N = 10.02%, Found C = 31.30%, H = 6.20%, N = 9.91%.









86

X-ray Crystallography. A crystal 0.05 x 0.07 x 0.13 mm

suitable for diffraction studies was mounted on the end of a

glass fiber and all subsequent measurements were made using a

Nicolet R3m diffractometer with graphite-monochromated Mo-Ka

radiation (X = 0.71069A). The cell dimensions were determined

by a least squares refinement of 25 automatically centered

reflections. A variable-speed (10 29.3*) 28 scan technique

was used to measure the intensity data from 0 to 450 degrees

in 28. Two standard reflections were measured every 98

reflections to monitor for any decomposition during the x-ray

analysis. No absorption correction was made. The pertinent

crystal data is given in Table 5-1.

Structure Refinement. The data reduction, structure

solution and final refinement were performed using the NRCVAX

(PC-Version)[18] package of programs. The Ru atom and all non-

hydrogen atoms were located by the heavy-atom method

(Patterson and Fourier syntheses) and refined anisotropically

by full-matrix least squares. The hydrogen atoms were located

by the calculation of a difference Fourier map and refined

isotropically. The model converged to an R of 0.027 and a Rw

of 0.034. The final positional parameters are given in Table

5-2. The final bond distances involving the non-hydrogen

atoms and bond angles are listed in Table 5-3. Table 5-4

lists the anisotropic thermal parameters and Table 5-5 lists

the hydrogen positional parameters.









87

Table 4-1. Crystal Data


formula

MW

a, A

b, A

c, A

a, deg

P, deg

Y, deg

Vol.,A3

z

Ocalc'g/cm3
space group
-1
p, cm1

no. of data used (Inet>2.5olnet)

Ra

b
w


RuC11N303H25Cl2

419.31

7.1907(12)

15.280(4)

7.8244(21)

90.305(22)

102.154(18)

89.895(18)

840.4

2

1.66

P Ibar

26.1

2603

2.7

3.4


R= I -I cI







R w(IFI-IFI) 2 1/2
E WIF2ol











Atomic Parameters x,y,z and Biso.


x/a y/b z/c Biso


Ru

Cll

01

N3

C2

C8

CL2

Cl

C3

C4

C5

C6

C7

C9

C10

ClI

N1

N2

W1

W2


.22152(2)


.21704(4)

.4133 (2)

.0130 (4)

.1059 (5)

.4176 (6)

.1037 (6)

-.2225 (2)

.4176 (6)

.3422 (8)

.4720 (6)

.4586 (7)

.2511 (7)

.1166 (6)

.2157 (8)

-.0126 (7)

-.0655 (6)

-.1857 (5)

-.0314 (5)

-.6733 (4)

.8546 (5)


.1624

.3004

.2994

.2803

.0868

.4335

.3321

.3153

.1922

.1207

.1021

.1292

.0059

.1303

.3574

.4155

.3589

.4531

.2259


.29801(4)


(1)

(2)

(2)

(3)

(3)

(1)

(3)

(3)

(3)

(3)

(3)

(3)

(3)

(3)

(3)

(2)

(3)

(2)

(2)


.5579

.1373

.4855

.1500

.2342

.7044

.3017

-.0332

.1874

.0508

-.0383

.0776

.3003

.3309

.2169

.1310

.3926

.6394

.7018


1.765(12)


(1)

(3)

(4)

(5)

(6)

(1)

(6)

(6)

(6)

(6)

(6)

(6)

(7)

(6)

(5)

(5)

(5)

(4)

(5)


3.05

2.54

2.27

2.56

2.88

3.31

2.79

3.83

2.60

3.51

3.39

2.63

4.08

3.17

2.28

2.91

3.01

3.13

3.84


(4)

(11)

(13)

(17)

(18)

(5)

(17)

(23)

(17)

(20)

(20)

(17)

(23)

(19)

(16)

(15)

(15)

(13)

(16)


Table 5-2.











Table 5-3. Bond Distances(A) and Angles()


Ru Cll
Ru 01
Ru N3
Ru Cl
Ru C2
Ru C4
Ru C7
Ru C8
Ru C10
01 Cll
N3 N2


Cll-Ru-01
C11-Ru-C2
C11-Ru-C8
Ru-01-Cll
Ru-C2-C1
01-Ru-N3
01-Ru-C2
01-Ru-C8
C3-C2-C4
Ru-C8-C9
N3-Ru-C2
N3-Ru-C8
C9-C8-C10
C2-C4-C5
C5-C6-C7
01-C11-N1
N1-C11-N2


2.3976(12)
2.102(3)
2.162(3)
2.219(4)
2.224(4)
2.230(4)
2.223(4)
2.230(4)
2.220(5)
1.267(5)
1.426(5)


C2 C1
C2 C3
C2 C4
C8 C7
C8 C9
C8 C10
C4 C5
C5 C6
C6 C7
Cl1 N1
Cl1 N2


159.70(8)
105.45(12)
87.80(12)
115.24(24)
71.15(24)
77.33(11)
84.35(14)
102.72(14)
124.1(4)
122.5(3)
120.20(15)
119.04(15)
122.4(4)
124.3(4)
111.2(4)
121.4(4)
118.2(4)


Cl1-Ru-N3
C4-Ru-C10
C7-Ru-C10
Ru-N3-N2
Ru-C2-C3
Ru-C2-C4
C1-C2-C3
C1-C2-C4
Ru-C8-C7
Ru-C8-C10
C7-C8-C9
C7-C8-C10
C2-Ru-C8
C4-C5-C6
C8-C7-C6
01-C11-N2
N3-N2-C11


1.423(6)
1.521(6)
1.417(6)
1.409(7)
1.508(7)
1.404(6)
1.514(6)
1.534(7)
1.514(6)
1.319(5)
1.345(5)


82.39(9)
127.80(17)
64.14(17)
108.58(22)
119.6(3)
71.67(23)
121.8(4)
113.6(4)
71.27(24)
71.21(25)
123.4(4)
114.0(4)
120.42(17)
111.4(4)
124.3(4)
120.4(4)
118.1(3)