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NEW CHIRAL FERROCENYLAMINE THIOETHER LIGANDS
AND THEIR APPLICATIONS TO CATALYSIS

presented by

Michael Onyekachi Okoroafor

has been accepted towards fulfillment I ‘
of the requirements for
I

Ph.D. degree in Chemistry

I
Major professor

Date November 14, 1985

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NEW CHIRAL FERROCENYLAMINE THIOETHER LIGANDS
AND THEIR APPLICATIONS TO CATALYSIS

Michael Onyekachi Okoroafor

A DISSERTATION

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

DOCTOR OF PHILOSOPHY

Department of Chemistry

1985

ABSTRACT

NEW CHIRAL FERROCENYLAMINE THIOETHER LIGANDS

AND THEIR APPLICATIONS TO CATALYSIS

By.
Michael Onyekachi Okoroafor

New chiral ferrocenylamine thioether ligands of the type, (fig)—
C5H5FeC5H3[CHMeNMe2][SR], R = Me, Et,i-Pr, n—Bu,i—Bu, _t_-Bu,_i_-Pentyl,
Ph, CHZPh, p-tolyl, 4-chlorophenyl, have been prepared by lithiation of optically
active N,N-dimethyl-1-ferrocenylethylamine followed by reaction with the
appropriate disulfide. These compounds are air-stable and were characterized
by use of spectroscopic techniques such as 1H and 13C NMR, infrared (IR)
and mass spectroscopy as well as elemental analysis. These chiral ferrocenylamine
thioethers readily chelate platinum and palladium chloride to form the chiral
heterobimetallic complexes, (_R_,§)-C5H5FeC5H3[CHMeNMe2][SR]/MCIZ,
(R = Me, _i_-Pr, fl-Pr, _i_-Bu, Ph, p-tolyl, 4-chlorophenyl; M = Pd, Pt). 1H NMR,
IR, MS and elemental analysis data were obtained for the chiral complexes.
An X-ray crystal structure of (R,§_)-C5H5C5H3[CHMeNMeZIISMeUPdClZ
was determined.

The catalytic applications of the chiral complexes were examined. The
chiral palladium thioether complexes are effective asymmetric Grignard

cross-coupling catalysts. The enantiomeric excess (e.e.) of the asymmetric

Michael Onyekachi Okoroafor

cross-coupling product was determined by 1H NMR spectroscopy in the presence
of a chiral shift reagent, Tris(d,d-dicampholylmethanato)europium(III), [Eu(dcm)3].
A possible mechanism of Grignard cross-coupling is proposed.

The complexes are also highly effective as selective hydrogenation catalysts,
converting dienes to monoenes at room temperature.

The chiral dialkyldithiocarbamate derivatives, (§,_S_)-C5H5FeC5H3[CHMe-
N Me2][SCSN R2], R = Me and Et, were prepared by reaction of (fi,R)—N,N-di-
methyl-lithioferrocenylethylamine with tetraalkylthiuramdisulfide. 1H and
13C NMR, IR, MS and elemental analysis data were obtained. Dynamic N MR
studies indicate that restricted rotation occurs around the carbamate carbon-
nitrogen bond in these derivatives and two conformers are present at low
temperature. Approximate rotational free energy barriers were determined

and were correlated with the "thioureide" band in the infrared.

All things are possible with

those who trust in God.

ii

DEDICATION

In Memory of Our Daughter, Ogechukwu.

iii

ACKNOWLEDGEMENTS

I sincerely appreciate the constant guidance, inspiration and
encouragement of Professor Carl H. Brubaker, Jr., throughout this work.

In addition, I would like to thank Dr. C.K. Chang and Dr. W.H. Reusch
for many helpful discussions. and Dr. L.D. Le, for technical expertise in
obtaining N MR spectra. My gratitude also to Dr. D. Ward for his assistance
in obtaining the X-ray structures.

1 would also like to thank Dr. Beth McCulloch, Dr. Robert V. Honeychuck,
Dr. Lie-Hang Shen and all the members of the group for their help and
friendship.

To our friends, especially Lewe Okereke, Ike and Chi Ononye, and our
God-daughter Katrina, I will always remain indebted.

Finally, my deepest gratitude goes to my wife, Ngozi, and her profound
love, unrivalled understanding, great patience, professional assistance in
interpreting some of my results and prayers throughout this work, and to

my mother and her love.

iv

LIST OF TABLES .............................................................................
LIST OF FIGURES ............................................................................
LIST OF SCHEMES. .................................................. . ......................
I. INTRODUCTION

[1. EXPERIMENTAL

A.

TABLE OF CONTENTS

Preparation of Ligands ............ .........................
(RFI-(dimethylaminoFethylferrocene, [(3)1] .....................

(§)—1-(dimethylamino-ethylferrocene, [(§_)-_7_] ........................

(R ,_S_)-l-(l-dimethylaminoethyl)—-2 ~methyl—thioferrocene,

(4__6, R: Me) ........... . .......................................................

(R, §)-l-(l—dimethylaminoethyl)-2-ethyl-thioferrocene,

(T_7_,R=Et) ..... ............. ...... . ............................ . .................

(_R,_S_)—1-(1-di methylaminoethyl)—2-isopropyl-thioferrocene,

(4—8-9 R =_I_"PI‘) eooeoeoeeeeooo oooooooooooooooooooooooooooooooooooooooooooooooooooooo

(R ,S)-l—(l-dimethylaminoethyl)-2-_r_1_-propylthioferrocene,

(_—_9, R = n-Pr) ...................................................................

(_ R ,_S_)-1 —( 1 -di methylam1noethyl)-2-t-butyl-th10f errocene,

(51,R = _t_- -.Bu) ............ .......................................... . ......

(R ,_S_)-1-(l-dimethylaminoethylFZ-isobutyl-thioferrocene,

(51, R- - _i_-Bu) ......... . .....................................................

(R ,_S_)-1 -(1-d1methylam1noethyl)-Z-n-butyl-thloferrocene,

(E2:- R= n‘BU) ooooo o eeeee oooeeeeee eeeeeeeeeeeee one. ooooo oooeeeoe eeeeeeee coo ooooo

(R ,_S_)-1-(1-dimethylaminoethylFZ-isopentyl-thioferrocene,

(Q, R - i-pent) ................... . .................... . ........................

(R,S)-1-—(l-dimethylaminoethylFZ-pehnyl-thioferrocene,

@711 = Ph) .....................................................................

(R ,_S_)-l-(l-dimethylaminoethylFZ-benzyl-thioferrocene,

(5:11, R: CHZPh) ............................................. . .................

00000000000 0.00....OIO..0O0..0OOOO..00..OI.0..OOOOOOOOOOOOOOOOOOOOOOO

Page
ix
xi

xiii

20
21
21

21
22
23
24
25
26
27
28
29
29

30

(R,S)-1—(1-dimethylaminoethy1)-2-(p-toly1)-thioferrocene,

(5312 = p-tolyl) ..................................................................
(fi,§)-l—(1-dimethylaminoethyl)-2-(4-chloropheny1)-

thioferrocene, (y, R = 4-chlorophenyl) ..................................
Preparation of Metal Complexes ............... . ...........................

Dichloro[(R_)-1—(S)-2-methylthioferrocenylethyldimethyl-
aminepalladium-(Ilkfl .........................................................

Dichloro[(_I_t_)-l —(S)‘-2-isopropylthioferrocenylethyldi methyl-
aminelpalladiumTII)-fl .........................................................

Dichloro[(_I_i_)-1-(S)-2-propylthiof errocenylethyldi methyl-
aminelpalladiumTII)-§p_ .........................................................

Dichloro[(fi)—1-(S)—2-isobutylthioferrocenylethyldimethyl-
aminelpalladium-(Ill-fil .........................................................

Dichloro[(R_)-1—(S)-2-phenylthioferrocenylethyldi methyl-
aminelpalladiumTII)-§2_ .........................................................

Dichloro[(§)-l-(_S_)-2-paratolylthioferrocenylethyldi methyl-
amine]-palladium(II)-§_3_ .......................................................

Dichloro[( R)-1 —(§_)-2-(4-chlorophenyl)thiof errocenylethyl-
dimethylamine]palladium(II)—6_4_ .............................................

Dichloro[(§_)-l ~(_S_)-2-(4-chlorophenyl)thioferrocenylethyl-
dimethylamine1palladiuman—Q ............................................

(R,§)-l-(1—di methylaminoethyl)—2-(dimethyldithiocarbamate)~
ferrocene, (gs) ....................................................................

(_R_LS_)-1-(1-dimethylaminoethyl)-2—(diethyldithiocarbamate)-
ferrocene, (67) ..... . ......................................................

Catalytic Applications of Complexes .....................................
i. Asymmetric Grignard Cross-Courpling Reactions ............
Grignard Cross-coupling Reaction of Allylmagnesium
Chloride to 4-phenyl-1-pentene Using Complexes §_8_,
_ffi, _6_2_, £53, or _6_4_ .........................................................

Conversion of 4-phenyl—1-pentene to methyl 3-phenyl
butyrate O.IO.IOOOOOOOOOOOOOOOOOOOOO0.... ..... O OOOOOOOOOOOOOOOOOOOO O 00000000 .0

vi

Page

31

32

33

33

34

34

34

35

35

36

36

36

37

38

38

38

39

Page

ii. Selective Hydrogenation of Conjugated Dienes to

Alkenes with §_8_, fl-6_5_ ............................................... 40
Hydrogenation of 1,3-cyclooctadiene with 5_8_, 92-64 in
acetone at 67 psi ....... . ......... . ..................................... 40
Solvent Effects on Hydrogenation of 1,3-cyclo-
hexadiene at Room Temperature .................................. 40
III. RESULTS AND DISCUSSION ....................................................... 44
A. (§,§)-C5H5Fecsn3[cHMeNMezllsal
(R: Me, Et, _i_- Pr, n-Pr, n-Bu, i- Bu, t— —Bu, Ph, CHZPh,
i-pent, p-tolyl, 4- Cl-Ph)_ ..... ............ . ..... . ........................ 44
1. Preparation ............................................................... 45
2. 111 NMR ..................................................................... 45
3. 13c NMR ............................ 57'
4. Infrared (IR) Spectra ................................................... 63
B. Palladium Complexes of (§,§)-C5H5FeC5H3[CHMeNMe2]-
[SR]
(R = Me, i—pr, _i_-Bu, Ph, p—tolyl) and Platinum Complexes of
(§,§)-C5H5Fecsu3lcHMeNMe2][s-4-01—Ph] ......... . ................ 64
1. Preparation ................................................................ 64
2. 1H NMR ..... ........................................................... 67
3. Infrared (IR) Spectra .................................................. 70
4. Structure of Dichloro[(R)-1-(_S_)—2- -methylthioferrocenyl-
ethyldimethylaminelpalladiumfll), 5_8 ........................... 70
c. (§,§)-C5H5re05H3[CHMeNMezltscsnnzl (R = Me,Et) ........... 98
1. Preparation ................................................................. 98
2. 1H NMR ............... . .................................................... 99
3. 13c NMR ............................................................... 102
4. Dynamic N MR Studies ................................................ 102

vii

D. Catalytic Application of Complexes . ...................................
'1. Asymmetric Grignard Cross-coupling Reactions ............

2. Selective Hydrogenation of Conjugated dienes to
Alkenes. ......................................................................

IV. APPENDIX ................................................................................

V. REFERENCES ............................................................................

viii

Page
111

111

118
127

131

Table

10

11
12
13
14
15

16

LIST OF TABLES

Chiral Ferrocenylphosphines for Asymmetric Catalysts ...........

250 MHz 1H NMR Data for (R ,_S_)-C5H5FeC5H3[CHMeNMe2]-
[SR]; R= Me, Et, _i_- Pr, n- Pr, n-Bu, _i_-Bu, _t_- -Bu, Ph, CHZPh,

_i_- -,Pent p-tolyl, 4- Cl—Ph ....... ... ...... ..... .......

250 MHz 130 NMR Data for (R ,_S_)—CSH5FeC5H3[CHMeNMe2]-

[SR] (4_6- 5_7) in CDClg/TMS at Room Temperature ............. . ........

250 MHz 1H NMR Data for (R,§)-C5H5Fec5H3ICHMeNMezl-
[SRllMClg Complexes (Si-Q) in CDCl3/TMS at Room

Temperature .0....0.00.00...O..0...O..00.00.0.0.........OOOOOOOOOOOOO OOOOOOOOOOOOOOOOOO

Metal-S, Metal-N, and Metal-Cl Stretching Modes in Several

Metal Complexes ........................ . .............................................

Positional Parameters and Their Estimated Standard Deviations
in Dichloro[(R)-1-(S)-2- -Methylthioferrocenylethyldimethyl-

aminelpalladiumflIT (_5__8) .............................. . ...........................

General Temperature Factor Expressions-B'S-for dichloro-
[(3)4-(_S_)-2-Methylthioferrocenylethyldimethylamine]-

palladiumfll). (_S_8_) ................................................... . ................
Refined Temperature Factor Expressions-Beta's- for g .............
General Temperature Factor Expressions-U'S for g ...................

Root-Mean-Square Amplitudes of Thermal Vibrations (in A)

for §8_ .....................................................................................
Bond Distances (A) for 5_8_ ....................................................
Bond Angles (in degrees) for §_§_ ................................................
Torsional Angles (in degrees) for E ...........................................
Least-squares Planes for _5_§_ ..... . ................................................

Dihedral Angles Between Planes in _5_8_ ........................................

Dehedral Angle and Bridgehead Angle of Selected [3]-

ferrocemphanes ............................................ . ..........................

ix

Page

16

47

58

66

68

74

76
77

78

79
80
82
86
95

97

97

Table Page

17 1H NMR Data for (R)— 7, (R ,_S_)-05H5FeC5H3ICHMeNMe21-
[R]: R: SCSNMez, 66 SCSNEtg, 67 C5H5Fe(C5H3 1-
CH2NMe2-2R), and C—5'H5FeC5H4R, R: SCSNMeg,
scsugtz ................................................................................. 100

13 13c NMR Data for (R)—7; (R ,SFC5H5FeCSH3ICHMeNMe21-
[R], C5H5Fe(C5H3-1-CH2NMez-2-;R) and .C5H5FeC5H4R;
R: SCSNMeZ, and SCSNEIZ ............................ . ....................... 103

19 NMR Parameters, Kinetic and Infrared Data for (R,§)—
C5H5FeC5H3ICHMeNM82HR]; C5H5Fe(C5H3-l-CH2NM62-

2R); and C5H5FeC5H4R; where R = SCSNMeZ, SCSNEt2 ............. 108
20 Asymmetric Grignard Cross-Coupling Reactions Using

Chiral Thioether Complexes ..... . .......... ....... .. ............... 113
21 Selective Hydrogenation of 1,3-Cyclooctadiene at Room

Temperature .................................... ...... .. ............... 119
22 Effect of Solvents on the Selective Hydrogenation of ,

1,3-Cyclohexadiene .................................................................. l 24

Figure

1

10

11
12
13

14

15

16

'17

LIST OF FIGURES

250 MHz 1H NMR Spectrum of i5: R = CHZPh ............................
250 MHz 1H NMR Spectrum of fl, R = 4-Cl-Ph ..........................
250 MHz 1H NMR Spectrum of 5_3, R =_i_-penty1 .........................
250 MHz 1H NMR Spectrum of _53, R = Ph .......... . .......................
Splitting Pattern of SCH2 Protons in _5_§_, R = i-pentyl ........ .. .......
250 MHz 1H NMR Spectrum of £5, R = p-tolyl. ............................
Gated Decoupled 13C NMR Spectrum of _5_7_ ...............................
Gated Decoupled 13C NMR Spectrum of§§ ...............................
250 MHz 1H NMR Spectrum of 19, PdClZ Complex . ....................

Structure and Numbering Scheme for C5H5FeC5H3-
[CHMeNMeZHSMel'PdCIZ 5_8_ ....................... ..........................

Stereoview of CsHsFeC5H3[CHMeNMeZIISMelPdClZ §§_ ...........
250 MHz 1H NMR Spectrum of Q, R = SCSNMeg .......................
Gated Decoupled 13c NMR of g3 ...............................................

Variable-Temperature 1H NMR Spectra of _6_6,
R = SCSNMez ..... . ....................................................................

Assignments of the Substituted Ring Carbons of Some
Substituted Ferrocenes ........... - ......... . .......................................

Assignments of Ring Carbons in Some Ferrocenyl
Carbamate Derivatives ............................................................

1H NMR Spectra of (_R) and (_S_)-methyl 3-phenyl butyrate
in the Presence of Increasing Concentrations of Chiral
Shift Reagent, Eu(dcm)3 ............. . ........ ................

xi

Page

51
52
53
54
55
60
61.
62

69

71
72
104

105
107
109

110

116

Figure
18

19

20

21

The Magnitudes of AM Increase for Methyl 3-Phenylbutyrate
With Decreasing Temperature in the Presence of Chiral Shift
Reagent, Eu(dcm)3 ............. . ............. . .......................................

Selective Hydrogenation of 1,3-Cyclooctadiene in Acetone
at 27°C and 67 psi Using Complex Q, R = Me .......... . ....... . ..........

Selective Hydrogenation of 1,3-Cyclooctadiene in Acetone
at 27°C and 67 psi Using Complex :33, R = Ph ............. . ................

Olefinic Region of 250 MHz 1H NMR of 1,3-Cyclooctadiene,

the Mixture of 1,3-Cyclooctadiene and Cyclooctene, and
Cyclooctene ............................................................................

xii

Page

117

120

121

122

Scheme

10

11

12

LIST OF SCHEMES

Some Characteristic Reactions of Dilithioferrocene ------

Selected Reactions of l-Dimethylaminomethyl-Z-lithio-

f errocene. .............................................. . ....................

Some Reactions of (R)-(_R_)-N,N-Dimethyl—l-lithioferro-

cenylethylamine. ........ ..................................

Some Reactions of (_S_)-(§)-N,N-Dimethyl-l—Lithioferro-

cenylethylamine. .. ............ . ............................ ..............

Reaction of Methyldisulfide with a t-butylester Enolate.

Reaction of Methyldisulfide with bis( n 6--phenyllithium)-

chromium. .........................................................................

Reaction of Tetraisopropylthiuram Disulfide with

Aryllithium Species. .............................................. . ............

Nucleophilic Substitution Leading to Ferrocenes with

Sulfur in the Side Chain. ......................................................

Introduction of Sulfur to a Ferrocene Ring by Electro—

philic Aromatic Substitution. ...............................................
Aminomethylation of Methylthioferrocene. ..........................

Asymmetric Hydrogenation by Using [(_S_)-(R)—BPPFA]. ............

Some Ferrocenylsulfide and Ferrocenylselenide Metal

Complexes. ........................................................................

xiii

Page

11

11

12

13

13

14

15

19

Scheme Page
13 Preparation Chiral Ferrocenylamine Thioether Ligands of
-the Type (R,_S_)-05H5FeC5H3[CHMeNMe2][SR]; R = Me,
Et, i—Pr, £431., n—Bu, L—Bu, t-Bu, i-Pentyl, Ph, CHzPh, p-tolyl
4-Cl-Ph. ............................................................................. 46
14 Preparation of Palladium Complexes of (R,_S_)-C5H5FeC5H3-
[CHMeNMeZIISR], (R = Me, i—Pr, n—Pr, i_-Bu, Ph, p-tolyl,

4-Cl—Ph) and Platinum Complexes of (R,_S_)-C5H5FeC5H3-

[CHMeNMeZIIS-4-Cl-Ph]. .................................................... 65
15 Preparation of (R,§)-C5H5FeC5H3[CHMeNMe2][SCSNR2],

R = Me and Et. ................... ................... .. ........... ....... 101
16 Proposed Mechanism for Grignard Cross—Coupling Reaction. 115'
17 Proposed Mechanisms for Homogeneous Selective Hydrogena-

tion of 1,3-cyclooctadiene via a 4-Coordinate intermediate-... 125

xiv

I. INTRODUCTION

INTRODUCTION

Ferrocene chemistry has generated much interest since its discovery in
1951,1 primarily due to stability and unusual reactivity. It readily undergoes
a variety of aromatic substitution reactions such as acylation, alkylation, formy-
lation, mercuration and sulfonation.2 Most of these substitution reactions
are electrophilic and are limited to electrophiles which do not oxidize the
iron atom or destroy the cyclopentadienyl ring—metal bond.
Metallation reaction complements electrophilic substitution in that it
provides an alternate route to introducing reactive functional groups on ferrocene.
Metallation may be achieved by the reaction of ferrocene with n-butylithium,
amylsodium or phenylsodium.3 Ferrocene is dilithiated in over 90% yield by
a mixture of fl-butyllithium and tetramethylethylenediamine (TMEDA).4 The
dimetallated species could be isolated as a pyrophoric red-orange crystals
where TMEDA chelates the dilithium reagent. Application of the lithium reagent
isolated as a pure solid, rather than the _i_1_1_ §_i_t_u slurry, results in higher yields

in the subsequent reaction with electrophiles.

'° (fig—mg»
l
E. E
z’ ‘z()z’ \z<
L_/ \___l

n-Bu Li
TM so A

 

>

<7?
©

In contrast to the dilithioferrocene, synthesis of monolithioferrocene by addition

of stoichiometric amounts of n—butyllithium/TMEDA to ferrocene results in

a mixture of monolithiated and dilithiated species.5 Another route to lithiofer—
rocene where alkyllithium is added to chloromercuriferrocene produces a reactive
dialkylmercury compound that forms undesirable side products.6 High yields

of lithioferrocene, with no concurrent dilithiation, is however obtained by

reaction of _n-butyllithium and bromoferrocene.7

 

Fe J‘BUU a T
at ..‘L

‘

Although the chemistry of ferrocene derivatives resembles that of benzene
derivatives, important differences between them arise, when the stereochemistry
of these systems is considered. The stereochemistry of metallocene derivatives
has generated much interest in the past.8‘12 This interest is due, in part,
to the recognition that ferrocene derivatives are chiral if one ring carries
two different substituents (5).11 Optical activity, however, arises because
there is no Sn axis.11113 Both the central and planar elements of chirality

could be manifested in such disubstituted ferrocene

 

<3?"

' z -—————-____..
F0 ' -——--—"""""‘
.5.

LAH

 

 

AsR, Cl 1.3F

 

PR Cl

9*...
e? .

. "T's @M:
Q
Q

PhLi Se 'fi fi
SiMe,CI R ,NCSSCNR

 

a;

 

F©e‘s¢\ seQSCNR. F‘
SR
0 Slide, ©Se/ S©SCNR R Me.;.p,.;.au,;-Pent

R : FILE!

HG

 

R=1MerEI,i Pf

Scheme 1: Some Characteristic Reactions of Dilithioferrocene.

" 20
QPH‘ _ Q5111“,
2
Fe . Fe "”92

 

Scheme 2: Selected Reactions of l-Dimethylaminomethyl-z-lithioferrocene

 

Scheme 3:

A620 (942-92

,.
“it.

' Fe Pphz

X

x:H.PRh2
(EMS-9189.2

n—BuLIII-lao’

 

X=H,PPh2
(El-(91381.35

Some Reactions of (RHRPNJ-Dimethyl-l-Lithioferrocenyl—
ethylamine.

 

 

 

Fe

(ii-(3)235.

Scheme 4: Some Reactions of (§H_S_)-N,N,-dimethyl-1-Lithioferrocenylethylamine

The organic chemistry of ferrocene and its derivatives is extensive and
literally thousands of reactions have been reported. One of the more recent
applications is their use as ligands in transition metal complexes.14‘16 Metalla-
tion has proved to be a useful synthetic technique for the introduction of potential
donors such as phosphines and arsines on to the cyclopentadienyl ring. Schemes
1,2,3 and 4 illustrate the variety of different donor substituents that may be
incorporated into ferrocene, dimethylaminomethylferrocene (6), and N,N—dimethyl-
-1-ferrocenylethylamine (7) respectively. Davison17 synthesized ferrocenylphos-
phines and ferrocenylarsines in high yield from 1,1'—di1ithioferrocene. Addition
of elemental sulfur to dilithioferrocene gave 1,2,3-trithia-[3l-ferrocene (9)
which can be reduced quantitatively to 1,1'-dithioferrocene (10). The selenium
analog (11) has also been reported.18

The [llferroceneophanes, which have phosphorus, arsenic or Group 6A
elements as the bridging atoms, are another interesting class of compounds
that have been obtained from the reaction of dilithioferrocene with RPClg,
RASC1219120 or RgMClz (M = Ge, R = Ph; M = Si; R = Ph, Cl)21 respectively.
These compounds exhibit unusual spectroscopic properties as the cyclopentadienyl
rings are severely tilted towards the bridge atom. Wrighton and co-workers
have used (1,1'-ferrocenediyl)dichlorosilane to derivatize a number of electrode
and silica surfaces by Opening the highly reactive, strained C-Si-C bond in
the ferrocenephane.22

The ferrocenophanes are cleaved by alkyllithium reagents to give a ring
opened ferrocenyllithium reagent. Subsequent reaction with electrophiles
gives rise to ferrocene derivatives with mixed functionality as in (15). Cullen20
has also reported to preparation of ring—substituted ferrocenophanes with phos-
phorus and arsenic bridges. These are precursors to chiral ferrocenes with

mixed functionality that have important applications in asymmetric synthesis.

Recently Gautheron23 reported the synthesis of new metalladiselenaferroceno-
phanes of the type Fe(n 5-C5H4Se)2M(n 5-C5H4R)2 (where M = Zr, Hf; R =

H, to -Bu) known as [3]ferrocenophenes.

So
e \ M/cpn
/ Wt

50

F

M = Zr, Hf; R =_t_-Bu, H

In solution at ambient temperature, these complexes appear to be non-fluxional
by a bridge reversal process and Show a staggered conformation of the ferrocene
moiety.

The coordination chemistry of _1_9 (Scheme 2, available from _1_8_ via nucleophilic
substitution of chlorodiphenylphosphine) with chormium, molybdenum, tungsten,
iron, and cobalt carbonyls has been investigated.14 The ligand was bidentate
with the group VIB carbonyls, but monodentate through phosphorus with Fe
and Co. Compound _1_§ adds in Grignard manner to carbonyl species giving
2_024125 and the addition products of acetylferrocene and acetaldehyde15126.
Pyridine undergoes a nucleophilic aromatic substitution to yield 23, whose
CoX2 complexes (X = Cl, Br, and SCN) have been studied.15

Marr and co—worker327 reported that _1_§_ reacts with paraformaldehyde
and dimethylformamide giving 1-dimethylaminomethyl-Z-hydroxymethylferrocene
and 1-dimethylaminomethyl-Z—formylferrocene, respectively. Several derivatives
of these compounds were reported. Trimethylchlorosilane reacts with _1_3 to
give _2_1_28 and 1a undergoes reaction with hexachloroethane to give the 2-chloro

compound.29 The latter reaction involves lithium-halogen exchange followed

by g-elimination giving tetrachloroethylene. Tri-n—butyl borate reacts with
lg to yield, after hydrolysis, boronic acid 21,30 which is an amino acid with

the same properties as natural amino acids: it has an isoelectric point and

is soluble in aqueous base and acid. More important, _21 undergoes replacement
of the boronic acid portion with Cl, Br, and I using cupric chloride, cupric
bromide and iodine as the reagents. Finally, various quinones have been added
to l_8_ giving the corresponding Keto—alcohols, eg., 36.31 An excess of quinone
was used and no evidence was found for addition of two molecules of _l_8_ to

the quinone.

Chiral ferrocenylphosphines32 are readily prepared by lithiation of optically
resolved N,N-dimethyl—1-ferrocenylethylamine _7_, followed by treatment with
chlorophosphines. The lithiation of (3)1 with n-butyllithium was previously
reported by Ugi and co-workers33 to proceed with high stereoselectivity to

give preferentially (R)-N ,N-dimethyl(-l-[(_R_)-2-lithioferrocenyll-ethylamine[(R)-—

(31-11.
H Li H
3 O
. NMO N M82
NMOz . l Li -‘ 2
Fe n Bu L ——>- F9

 

*Q

(fil-(fil-gzum) (El-(glaze (4%)

@—

Q

(5)12,

10

(R)—N,N-dimethyl-1-[(§)-2-(diphenylphosphino)ferrocenyl]—amine [(R)-(§)—PPf A]
(Q) and (_S_)-N,N-dimethyl-l-[(§)-2-(diphenylphosphino)ferrocenyl]ethylamine,
[(§)-(_R)-PPfA] (_3_§_), was obtained in high yield from (R)-(R)-_21 and (§_)-(_S_)-_2_8
respectively. The stepwise lithiation of (IQ-1 or (§)-7_ with fl-butyllithium,

in ether and with _n-butyllithium/TMEDA followed by treatment with chlorodi-
phenylphosphine led to the introduction of two diphenylphosphino groups, one
onto each of the cyclopentadienyl rings to give (R)-N,N-dimethyl-1-[(_S_)-1',2-bis-
(diphenylphosphino)ferrocenyl]ethylamine, [(R)-(_S_)-BPPfA] (39) or (_S_)-N,N-dimethyl-
-1-[(R)-1',2-bis(diphenylphosphino)—ferrocenyl[ethylamine[(_S_)-(R)-BPPfA](3_7_).

The analogous bis(dimethylphosphine) derivatives were also prepared. The
preparation of (SHEFE was achieved by transmetallation of (§)~N,N-dimethyl-
1-[(B)—2-(trimethylstannyl)-ferrocenyl]ethylamine 2_6_ that had once been isolated
as a precursor for lithioferrocene (§)-(_S_)-§.34 The acetate (R)-(§)-_3_l_ was
converted quantitatively into a ferrocenyl phosphine with the hydroxyl group,
(R)-1-1[(_S_)-1',2-bis(diphenylphosphino)ferrocenyl]ethanol, [(R)-(§)-BPPfOH],
(R)-(§)-§_4, and (IQ-1-[(S)-2-dipheny1phosphine]ferrocenyllethanol [(R)-(_S_)-PPfOH]-
(_11)-(_S_)-_3_3_.

So far it is obvious that there are a multitude of electrophiles that will
react with lithioferrocenes 2, £3, 2_7_, and 2_8_. There are also many lithiated
compounds that will react with disulfides and diselenides.

The reaction of disulfides with anions has been known for many years,
and involves electrophilic rather than nucleophilic sulfur. In organic chemistry,
the reaction is used with enolate anions to produce a-sulfenyl carbonyl species
(Scheme 5), intermediates on the path to a, B -unsaturated carbonyl

compounds.35"37

ll

..., D
(7 "fun"

MeSSMe ) CO ‘-"

 

 

Scheme 5: Reaction of Methyldisulfide with a _t_-butylester Enolate

In 1981, bis( nS-benzene)chromium was lithiated and the product reacted

with methyl disulfide (Scheme 6)”.

Q
(Q

 

MaSSMe % 9’

93

Scheme 6: Reaction of Methyldisulfide with bis( ns-phenyl Lithium) Chromium

Thioether sandwich complex _33 acted as a chelating agent with Mo(CO)4.
Cava's group39 has found that phenyllithium and a number of lithiated aromatics
react with tetraisopropyl thiuram disulfide to give S-aryl-N,N-diisopropyldithio—
carbamates (fl, Scheme 7). The bulk of the isoprOpyl groups prevents attack
at the thione carbons, in contrast to the tetramethyl analog. With tetraisopropy-

lthiuram disulfide replaced by tetramethylthiuramdisulfide, a major side product,

12

thioamide, results.

 

.7 )—
#) ArSCN

_{NZSSENT’ ArLi. g )-
52

Scheme 7: Reaction of Tetraisopropylthiuram Disulfide with Aryllithium Species

The authors hydrolyzed dithiocarbamates, 19 to the thiols in high yield, so
that the sequence represents a new synthesis of aromatic thiols.

Recently in our laboratory,‘“"42 it was found that lithioferrocene and
1,1'-dilithioferrocene react with various disulfides to give thioethers 16 and
dithiocarbamates _1_7_ (Scheme 1). Other ferrocene derivatives with sulfur in
side chains have been made, but these were the products of a nucleophilic
substitution in the side chain (Scheme 8) or electrophilic sulfonation (Scheme
9). Reaction of tetraalkylammonium iodide fl (Scheme 8), with sodium sulfide
gave thioether 12 and disulfide £3.43 Sulfur was introduced directly to a ferrocenyl
ring via electrophilic sulfonation (Scheme 9).44 Sulfonic acid 44 was converted
to the sulfonyl chloride and then the thiol. The thiol was converted to its
methyl thioether. The methyl thioether (fl, Scheme 10), was subjected to

electrophilic substitution with bis(diomethylamino)methane45.

13

pn
2C0” + PhZCOH p
CH NM 1' “26°"
2 e3 Na 3 Cst
Fe ‘2) + (=st
© Fe Fe
41 :3): 2 ©
— 2
42 43

Scheme 8: Nucleophilic Substitution Leading to Ferrocem with Sulfur in the
Side Chain

 

Fe 3
Ac —)

<E§:;> 0180 H <E§E;>_s°3“
@
4

Scheme 9: Introduction of Sulfur to a Ferrocene Ring by Electrophilic
Aromatic Substitution

©SM° Q5“ 95"-
. Me NCH Hide
2 2 2 ' .4. Me N .
Fe HOAc ) Fe NMez 2 Fe +

45

@534:

Fe

§ NMe2

Scheme 10: Aminomethylation of Methylthioferrocene

All three possible monosubstituted products were obtained as was expected
from the activating nature of the methylthio group. The lithiation procedure
yielding _1_8_, 17., and 2_8_, described previously, offers a distinct advantage over
electrophilic substitution in that only a single lithiation product is obtained.
Symmetrically 1,l’-disubstituted ferrocenes Fe( n 5-C5H4E), where E is
a potential electron donor such as phosphine or arsine, have generated much
interest in functioning as rigid chelating ligands.4’16’17’46'43 In particular,
1,1'—bis(diphenylphosphino)-ferrocene (fdpp) strongly chelates Ni and Pd and
such complexes have been shown to exhibit extremely high catalytic activity
for selective cross-coupling reactions.49 Hughes50 and Christenson51 have
reported that fdpp complexes of rhodium are highly selective hydroformylation
catalysts. Brubaker and co-workers‘m’41 has reported the properties of some
1,1'-bis(thioether)ferrocene derivatives. We have also reported that the Pd

complex of dimethylaminomethylferrocenyl sulfide is an efficient selective

15

hydrogenation catalyst.52

Another recent development in ferrocene chemistry is the use of chiral
ferrocene derivatives as ligands in transition metal catalyzed asymmetric
synthesis. Rhodium and palladium complexes with chiral ferrocenylphosphine
ligands have been used as catalysts in asymmetric hydrogenation,55‘62 Grignard
cross-coupling55i63‘70 and hydrosilylation reactions55’71’73. In particular,
acylamino acids have been produced in 93% optical purity by the asymmetric
hydrogenation of a-acetaminocinnamic acids catalyzed by a rhodium complex
of (§)-N,N-dimethyl-1-[(§_)-1',2-bis(di-phenylphosphino)ferrocenyl]ethylamine.

[(§_)-(_13_)-BPPfA] (Scheme 1 1).

 

Pb uncom- "2 uncom-
\c = c/ a Pncuzcu
H/ \COOH (5-)'(3-)‘3”W 9" coon

931:2; (Ed-'0"!
Scheme 11: Asymmetric Hydrogenation by Using [(_S_)—(_R)—BPPFA]

Table 1 shows a number of various possible ligands - mostly bidentate phosphine
derivatives. N,N-dimethyl-l-[2-(diphenylphosphino)ferrocenyl]-ethylamine
(PPFA) is the parent member of the ferrocene derived ligands. It has two

kinds of chirality, one on the side chain (central element of chirality) and a

second on the 1,2-disubstituted cyclopentadiene ring.

Ligand

Pth

O Nsz

 

Abbreviation

FcPN

FcPPfl

1

G

0')

Ligand

 

 

(M)

'0; E“ I

p

3‘

 

Pth

Pth

th

I’"2

Abbreviation

BPPFOH

PPEF

BPPEF

(l-(Z-(DiphenylphOSph
no)ferrocenyl)ethyl)g€

ghenzlghOSthne

Table l. Chiral Ferrocenylphosphines for Asymmetric Catalysts.

17

u, I

Me
@5192 ____________.

I'l'e Pth -———--—"""

@

 

 

(3)-(§_)-PPFA

The aim of this research was to develop a new class of chiral chelating
ferrocenyl thioether ligands. The recent interest in transition metal sulfides
led to the investigation of the preparation and application of ferrocenyl thio
and seleno ethers.52

A few ferrocenyl thioether complexes are known. Pauson44 has reported
synthesis of methylthioferrocene from ferrocenesulfonic acid whereas Russian

workers74 prepared this complex from thiocyanatoferrocene

Feso3H_., FeSOZCI—FeSH

\
FeSMe
/

FeHgCl ——,FcSCN

Ferrocenylmethylsulfides have also been prepared from ferrocene and mercaptans

in one step syntheses.75

HC104
FeH + HSR _——’ FCCstR

18

These procedures are limited to the preparation of specific ferrocenylsulfide
complexes. A new synthetic method“,52 has been developed similar to that
reported by Elschenbroich38). This procedure is a one-pot, high yield general
synthesis of substituted ferrocenylsulfides and has been applied in this work.

Some metal complexes of these new ferrocenyl thio ether chelating ligands
have been prepared and their application as catalysts for selective hydrogenation
and asymmetric Grignard cross-coupling reactions examined.

In addition the reaction of tetraalkylthiuram disulfides with _2_'_I_ was examined.

(CO), 19

 

 

F.e >< F|e Pd-Pi’h,
O 5‘ ...
O (20)) © 5
“1(‘3 0)‘2 Pd (PPhJ‘

@E
Fe \E

©E/
as

Fe 2 '
@- EH
E Me,MCl,
T.C|‘ NEt
E 3 5.50 1
© @E .
E\ l \ [Me
Fe X Fe M\
Me
@E/ ©¥
X = Se,1l’e "' ‘ Si,60.$n,C

Scheme 12: Some Ferrocenylsulfide and Ferrocenylselenide Metal Complexes

II. EXPERIMENTAL

EXPERIMENTAL

Air sensitive reagents were manipulated in prepurified argon or nitrogen
atmosphere. Standard schlenk-tube techniques and vacuum line were employed.
Where necessary a nitrogen-filled glovebox was used for transfers.

Infrared spectra (IR) were obtained by use of a Perkin-Elmer 457 grating
spectrophotometer or a Perkin-Elmer 599 grating spectrophotometer by using
neat films of liquid samples, N ujol mulls between CsBr plates or in KBr pellets
for solid samples. Ultraviolet and visible spectra (UV-VIS) were recorded by
use of a Cary 17 spectrophotometer and acetonitrile solutions. Mass spectra
(MS) were obtained by means of a Finnigan 4000 instrument with an Incos data
system at 70 eV. Optical rotations were determined with a Perkin-Elmer ‘141
polarimeter. Elemental analyses were performed by Galbraith Laboratories,
Knoxville, Tennessee. Gas chromatography (CO) was carried out by using
a Hewlett—Packard 5880A instrument.

All melting points were determined by using a Thomas-Hoover capillary
melting point apparatus and were uncorrected.

Proton N MR spectra were obtained by use of a Bruker WM-250 spectrometer
at 250 MHz in chloroform-d1 solutions with chemical shifts reported in parts
per million downfield from a tetramethylsilane internal standard. Carbon-l3
NMR (broadband proton decoupled and gated decoupled) were obtained by
use of a Bruker WM-250 spectrometer. at 62.9 MHz. A pulse width (PW) of
8 us and a relaxation delay (RD) of 63 were generally employed.

‘ All solvents used were A-C-S reagent grade and were distilled by standard
methods76 before use. (_B_)-N,N-dimethyl-l-ferrocenylethylamine(§-7) and
.(_S_)-N,N—dimethyl-1-ferrocenylethylamine (§-7) were prepared according to

Ugi's procedure.77 Dimethylaminomethyl ferrocene (6) was made by the standard

20

21

method.78 Bis(benzonitrile) complexes, [(PhCN)2MC12] where M = Pd, Pt,
were prepared according to published procedures.79v80 The hydrogenation
substrate 1,3-cyclooctadiene was obtained from Columbian Carbon Co., 1,3-cyclo-
hexadiene was obtained from Columbian Organic Chemical Co., and cyclohexene
was obtained from Aldrich Chemical Co. These reagents were retreated by
standard methods before use. The Grignard cross-coupling substrate, 1—phenylethyl
chloride, was prepared as previously reported;81 allylmagnesium chloride (2
_M_ solution in THF) and allylmagnesium bromide (1 _IV_I_ solution in ether) were
obtained from Aldrich Chemical Co. The 1H NMR chiral shift reagents, Tris(d,d—
dicampholymethanato)europium(III) [Eu(dcm)3], was obtained from Alfa Products.
A pressure bottle with gauge was used to perform hydrogenations.

X-ray structure determinations were performed on a Nicolet P3P computer
controlled 4-circle diffractometer equipped with a graphite crystal incident

beam monochromator.

A. Preparation of Ligands
(R)-l -(Dimethylamino)-ethylferrocene[(_l}_)-7l and (S)-l-(Dimethylamino)-ethyl-

ferrocene [(_S_)-7 1.

N,N-dimethyl-1-ferrocenylethylamine (7) was prepared and resolved by
using (§)-(+)tartaric acid as described by Ugi.77 The (_13_)-(+)amine tartarate
crystals were recovered from the mother liquor by treatment with diethylether
and then recrystallized three times from 10:1 acetone:water, allowing about
17 mL of solvent for each gram of salt. The (_S_H-)amine tartarate crystals
filtered off readily as previously reported.77 The tartarate salts were dissolved
in 20% aqueous NaOH solution and extracted with methylene chloride. The
amine solutions were dried over anhydrous K2003 and evaporated to give
a dark brown oil that partially solidified on cooling. [ml];25 + 14.1° for (3)4—

(dimethylamino)-ethylferrocene [(3)4], and [aJDZ5 - 14.1° for (_S_)-1—(dimethyl-

22

amino)—ethylferrocene [(_S_)-7], lit.2 [(111325 + 14.1° and -14.1°, respectively.

MS m/e (relative intensity), 257 (83, M+), 242 (95, M+-Me), 213 (100, M+-NMe2),
212 (36, M+-HNMe2), 121 (66, FeCp), 72 (18, CHMeNMez), 65 (3, Cp), 56 (21,
Fe), 44 (4, NMez). 1H NMR ( (Sppm) 4.11 (m, 4H, 05H4); 4.08 (s, 5H, Cp); 3.60
(q, J = 6.8 Hz, 1H, CH); 2.09 (s, 6H, NMeZ); 1.46 (d, J = 6.8 Hz, 3H, NCHCH3).
13c NMR (6 ppm) 86.2 (s, CI); 68.5 (d, J = 91 Hz, 02-5), 67.7 (d, J = 88 Hz,

Cp); 66.5 (d, J = 92.4 Hz, C2, c3, c4, C5) 66.3 (d, J = 9.2 Hz, C2, c3, c4, (:5);
65.9 (d, J = 91.4 Hz, CZ, C3, C4, 05); 57.8 (d, J = 67.3 Hz, NCH); 40.2 (q, J

= 47.4 Hz, NMeg); 14.8 (q, J = 42.9 Hz, NCHME).

(_R_,§)—1-(1-Dimethylaminoethyl)-2-methylthioferrocene (46, R=Me).

The amine (3)11 (1.5 g, 5.8 mmol) was dissolved in 50 mL dry ether and
placed in a 100 mL round-bottomed schlenk flask equipped with a side arm
and rubber septum. The solution was cooled to -78°C and while being stirred
4.0 mL (6.4 mmol) of _q-BuLi was added dropwise via a syringe. The orange
suspension was allowed to reach room temprature and stirred overnight. M8232
(0.53 mL, 5.9 mmol) was added dropwise via syringe at -7 8°C. The solution
was allowed to reach room temperature and stirred under N2 for 24 h. After
refluxing for 7 h, the reaction mixture was cooled and then 20 mL of saturated
aqueous NaH003 was added. The resulting organic layer and ether extracts
from the aqueous layer were combined, washed twice with ice water, dried
over anhydrous NaZSO4, and evaporated to give a dark oily residue. The oil
was chromatographed on alumina by eluting first with hexane and then with
CH2012 to give the product which upon recrystallization from hexane/petroleum
ether gave yellow crystals: yield 65%; mp 64-66°C; MS m/e (relative intensity),
303 (19, Mt), 213 (100, M+-NMe2), 121 (92, FeCp), 72 (57, CHMeNMeZ), 56
(60, Fe). IR (Nujol, 051) 1260 (C-N stretch), 1104, 1092 (asymmetric ring breathing),

988 (ring-H bend parallel to ring), 810 (ring-H bend perpendicular to ring),

23

450 cm'1 (asymmetric ring-Fe stretch). 1H NMR (6 ppm) 4.28 (m, 1H, H3,
H4, H5); 4.18 (m, 1H, H3, H4, H5); 4.17 (m, 1H, H3, H4, H5); 4.10 (s, 5H, Cp);
3.94 (q, J = 7 Hz, 1H, NC_I‘_I_); 2.30 (S, 311, SCH3); 2.13 (S, 6H, NMez); 1.40 (d,
J = 7 Hz, 3H, NCHgI-lg).

13c NMR (6 ppm) 84.0 (s, C2); 75.1 (5, CI); 71.0 (d, 03, c4, C5); 69.9 (d, Cp);
67.3 (d, C3, (:4, cs); 66.5 (d, 03, c4, Cs); 56.1 (d, NCH); 40.5 (q, NMez); 19.8
(q, SCH3); 13.1 (q, NCH_(_3_};I_3).

Anal. Calcd. for 015H21FeNS: C, 59.41; H, 6.93.

Found: C, 59.54; H, 6.89.

(fi,§)—1{DimethylamhnethyD-Z-ethylthioferrocene(fl, R = Et).

The amine (IQ—1 (1.5 g, 5.8 mmol) was dissolved in 50 mL dry ether and
placed in a 100 mL round-bottomed schlenk falsk equipped with a sidearm
and rubber septum. The suspension was cooled to -7 8°C and while being stirred
4.0 mL (6.4 mmol) _r_l_-BuLi was added dropwise via a syringe. The orange suspension
was allowed to reach room temperature and stirred overnight. Et2S2 (0.73
mL, 5.9 mmol) was added dropwise via a syringe at -7 8°C. The solution was
allowed to reach room temperature and stirred under N 2 for '24 h. After refluxing
for 7 h, the reaction mixture was cooled and 20 mL of water added. The organic
layer was separated, dried and evaporated to give a brown oil. The oil was
chromatographed on alumina by gradient elution (hexane/ether/ CH2C12), giving
a brown oil: yield 45%; MS m/e (relative intensity), 317 (53, Ml“), 302 (23,
M+-CH3), 272 (44, M+-HNMe2), 121 (29, FeCp), 72 (9, CHMeNMeZ), 56 (17,
Fe), 40' (100).
IR (neat, KBr) 1360 (C-N stretch), 1100, 1000 (asymmetric ring breathing—
unsubstituted ring), 452 cm‘1 (asymmetric ring-Fe stretch).
1H NMR (6 ppm) 4.20 (m, 3H, C5H3; 4.10 (s, 5H, Cp); 3.95 (q, J = 7.0 Hz, 1H,

-c_H-); 2.75 (q, 1H, CHZCHg); 2.60 (q, 1H, CH2CH3); 2.10 (s, 6H, NMeg); 1.35

24
(d, 3H, -CHCH3); 1.15 (t, 3H, CHZCH3).

(§,_S_)-l-(l-Dimethylaminoethyl)-2—isopropylthioferrocene (_4_§_, R = j-Pr)

The amine (_R_)-_7_ (1.5 g, 5.8 mmol) was dissolved in 50 mL dry ether and
placed in a 100 mL round-bottomed schlenk falsk equipped with a side arm
and rubber septum. The suspension was cooled to -7 8°C and while being stirred
4.0 mL (6.4 mmol) of _n_—BuLi was added dropwise via a syringe. The orange
suspension was allowed to reach room temperature and stirred overnight.
Then 0.94 mL (_i_-Pr)252 (5.9 mmol) was added dropwise via a syringe at -78°C.
The reaction mixture was allowed to reach room temperature and stirred under
N2 for an additional 24 h, after which saturated aqueous NaHCO3 was added
to the mixture. The resulting organic layer and ether extracts from the aqueous
layer were combined, washed with cold water and dried over anhydrous NaZSO4.
Evaporation of the solvent gave a product mixture which was chromatographed
on a silica gel column (hexane/ether) to give orange crystals. The product
was recrystallized from hexane to give bright orange needles: yield 80.4 96;
mp 34-3500. MS m/e (relative intensity), 331 (85, W), 316 (25, M+-Me), 287
(35, M+-NMe2), 286 (60, M+-HNMe2), 244 (48, M+-CHMeNMe2), 210 (5, M+-CpFe),
121 (78, FeCp), 56 (35, Fe), 43 (100,_i_-Pr).
IR (neat, KBr), 3096 (ring-H stretch), 2870, 2820, 2778, 2930 (alkyl C-H stretch),
1450, 1380 (methyl C-H bond), 1260, 1245 (alkyl C-H bend), 1190 (C-N stretch),
1103, 1090 (asymmetric ring breathing), 998, 930 (ring-H bend parallel to ring),
815 (ring-H bend perpendicular to ring), 532 (asymmetric ring tilt), 465 cm'1
(asymmetric ring-Fe stretch).
1H NMR (6 ppm), 4.33 (m, 1H, H3, H4, H5); 4.21 (m, 1H, H3, H4, H5); 4.17
(m, 1H, H3, H4, H5); 4.09 (s, 5H, Cp), 4.00 (q, J = 7.0 Hz, 1H, -cgNMe2); 3.20
(m, J = 7.0 Hz, 1H, SCHMez): 2.12 (s, 6H, NMeZ), 1.34 (d, J = 7.0 Hz, 3H, NCHCHg);

1.22 (d, J = 7.0 Hz, 3H, 8 CH3); 1.15 (d, J = 7.0 Hz, 3H, 8 CH3).

25

13c NMR (6 ppm), 94.6 (s, C2), 78.3 (s, CI); 75.2 (d, J = 91.0 Hz, 03, c4, (:5);
69.9 (d, J = 97.4 Hz, Cp), 67.8 (d, (:3, (:4, cs); 66.7 (d, 03, c4, 05); 55.8 (d,

J = 66.5 Hz, N_(_:_H); 39.9 (q, NMez), 39.2 (d, J = 63.0 Hz, SCH); 23.8 (q, J =
38.0 Hz, 8 Q3), 22.6 (q, J = 39.0 Hz, 853th 10.6 (q, J = 39.2 Hz, NCHgHg).
Anal. Calcd. for C17H25FeNS: C, 61.63; H, 7.55; S, 9.67.

Found: C, 61.70; H, 7.75; S, 9.90.

(§,§)-1-(1-DimethylaminoethyI)-2-g-propylthioferrocene (32, R = g-Pr).

The procedure was the same as for 43, R =_i_-Pr, except that 0.92 mL (5.9
mmol) of (fl-Pr)2S2 was added. The product was recrystallized from hexane/CH2-
C12 to give dark organe crystals; yield 65%, mp 32-33°C. MS m/e (relative
intensity), 331 (100, M+), 316 (36, M+-Me), 288 (13, Mtg-Pr), 287 (48, M+-NMe2),
286 (71, M+-HNMe2), 256 (5, M+-S-n_-Pr), 210 (5, M+-FeCp), 121 (17, FeCp),

65 (3, Cp), 56 (7, Fe), 43 (38, fl-Pr), 41 (62, CH2=CHCH3).

IR (neat KBr), 3096 (ring—H stretch), 2830, 2870, 2850, 2818 (alkyl C—H stretch),
1454 (CH2 scissoring of SCHg), 1362 (methyl C-H bend), 1260, 1245 (alkyl

C-H bend), 1190 (C-N stretch), 1152 (C-H deformation), 1104 (asymmetric

ring stretch), 998, 970 (ring-H bend parallel to ring), 815 (ring-H bend perpendicular
to ring), 454 cm‘1 (asymmetric ring-Fe stretch).

1H NMR (6 ppm), 4.32 (m, 1H, H3, H4, H5); 4.19 (m, 1H, H3, H4, H5); 4.16

(m, 1H, H3, H4, H5); 4.10 (s, 5H, Cp); 3.97 (q, J = 7.0 Hz, NC_I_I_CH3); 2.77 (m,

1H, SCHZ); 2.58 (m, 1H, SCHg); 2.12 (s, 6H, NMez); 1.56 (m, 2H, BCHZ); 1.36

(d, J = 7.0 Hz, 3H, NCHCH3); 0.95 (t, J = 7.1 Hz, 3H, y CH3).

130. NMR (6 ppm), 93.2 (s, 02); 80.5 (s, C1); 73.3 (d, J = 95.8, c3, c4, c5);

69.9 (d, J = 92.4, Cp); 67.4 (d, J = 92.6, c3, c4, C5); 66.5 (d, J = 92.4, c3, c4,
05); 55.9 (d, J = 71.4, N_(_3HMe); 40.2 (q, J = 51.9, NMeg); 38.7 (t, J = 58.0, SCHZ);
22.9 (t, J = 43.0, 8 CH2); 13.5 (q, J = 37.0, 7 CH3); 12.0 (q, J = 42.5, NCH—2H3).

Anal. Calcd. for C17H25FeNS: C, 61.63; H, 7.55.

26
Found: C, 61.90; H, 7.62.

(§,§)-l-(1-Dimethylaminoethyl)-2-1—butylthioferrocene (39, R = _t_-Bu)

The amine (3)27 (1.0 g, 3.9 mmol) was dissolved in 40 mL dry ether in
a 100 mL round-bottomed schlenk flask equipped with a side arm and rubber
septum. The suspension was cooled to -7 8°C and while being stirred 1.8 mL
of 2.7 _N_I_ fl-BULI (4.8 mmol) was added dropwise via a syringe. The orange
suspension was allowed to reach room temperature and stirred overnight.
Then 0.78 ng_t_—Bu282 (4.0 mmol) was added dropwise via a syringe at -7 8°C.
The reaction mixture was allowed to reach room temperature and stirred under
N2 for an additional 24 h, after which saturated aqueous NaHCO3 was added
to the mixture. The resulting organic layer and ether extracts from the aqueous
layer were combined washed with cold water and dried over anhydrous K2C03.
Evaporation of the solvent gave a brown oil that was chromatographed on
a silica gel column by eluting first with hexane, then with ether and finally
with MeOH. The product obtained was orange oil: yield 64%.
MS m/e (relative intensity), 345 (35, M“), 301 (5,M+-NMe2), 300 (5, M+-HNMe2),
244 (100, M+-_t_-Bu-NMe2), 121 (131, FeCp), 89 (4, S-_t_-Bu), 57 (33, t—Bu), 56
(15, Fe).
IR (neat, CsI), 3100 (ring C-H stretch), 2960, 2940, 2860, 2820 (alkyl C-H stretch),
1450 (asymmetric C-H bend), 1390, 1370 (symmetric C-H bend of CH3), 1260,
1245 (alkyl C-H bend), 1190 (C-N stretch), 1000, 930 (unsubstituted ring stretch),
818 (ring C-H bend perpendicular to ring), 656 (C-S stretch), 468 cm‘1 (asymmetric
ring-Fe stretch).
1H NMR (6 ppm); 4.41 (m, 1H, H3, H4, H5); 4.25 (m, 1H, H3, H4, H5); 4.21
(m, 1H, H3, H4, H5); 4.08 (s, 5H, Cp), 3.88 (q, J = 6.9 Hz, 1H, NCHMe); 2.12
(s, 6H, NMeg); 1.30 (d, J = 6.9 Hz, 3H, NCHCH3); 1.24 (s, 9H, 8CH3).

13c NMR (6 ppm), 95.5 (s, C2); 77.8 (s, cl); 77.7 (d, J = 94.1 Hz, C3, 0),, cs);

27

70.8 (d, J = 88.9 Hz, Cp); 68.9 (d, J = 90.3 Hz, 03, 0),, cs); 68.2 (d, J = 91.7
Hz, C3, C4, C5); 55.9 (d, J = 68.4 Hz, NgHMe), 45.9 (S, SE); 39.9 (q, J = 51.6
Hz, NMeg); 31.7 (q, J = 41.5 Hz, 8 CH3); 9.3 (q, J = 42.0 Hz, NCH_C_3_I_I_3).
Anal. Calcd. for C13H27FeNS: c, 62.61; H, 7.83.

Found: C, 62.70; H, 8.00.

(_1_l_,§)-1-(1-Dimethylaminoethyl)—2-isobutylthioferrocene (_51, R = _i-Bu)

The procedure was the same as for 5_0_, R = _t_-Bu, except that 0.75 mL
(4.0 mmol) of _i_-Bu2S2 was used. The product was obtained as brownish orange
oil: yield 84.596.
MS m/e (relative intensity), 345 (80, W), 330 (28, M+-Me), 301 (38, M+-NMe2),
300 (42, M+-HNMe2), 256 (3, M+-S-_i_-Bu), 244 (24, M+-NMe2-_i_-Bu), 121 (36,
FeCp), 89 (6, S-i—Bu), 72 (100, HCMeNMez), 65 (5, Cp), 57 (26,_i_-Bu), 56 (48,
Fe), 45 (16, HNMeg), 44 (34, NMeZ).
IR (neat, CsI), 3100 (ring C—H stretch), 2960, 2940, 2870, 2820 (alkyl C-H stretch),
1460 (asymmetric C-H bend), 1383, 1365 (symmetric C-H bend of methyl),
1260 (alkyl C-H bend), 1190 (ON stretch), 1106 (asymmetric ring breathing),
1000 (unsubstituted Cp ring stretch), 818 (ring C-H bend perpendicular to ring),
532, 496 (asymmetric ring tilt), 452 cm‘1 (asymmetric ring-Fe stretch).
1H NMR (6 ppm), 429 (m, 1H, H3, H4, H5); 4.17 (m, 1H, H3, H4, H5); 4.13
(m, 1H, H3, H4, H5); 4.10 (s, 5H, Cp); 3.97 (q, J = 7.0 Hz, 1H, NCHMe); 2.72
(dd, Jgem = 12.0 Hz, Jvic = 6.0 Hz, 1H, SCfig); 2.47 (dd, Jgem = 12. Hz, Jvic
= 8 Hz, 1H, 8%), 2.12 (s, 6H, NMez); 1.76 (M, 1H, 8 CH); 1.35 (d, J = 7.0
Hz, 3H, NCHQH3); 0.99 (d, J = 7.0 Hz, 3H, YCH3); 0.93 (d, J = 7.0 Hz, 3H,
YCH3).
13c NMR (6 ppm), 93.2 (s, C2); 80.8 (s, CI); 73.2 (d, J = 88.1 Hz, 03, c4, 05);
69.9 (d, J = 84.5, Cp); 67.4 (d, J = 84.5 Hz, C3, C4, C5); 66.5 (d, J = 84.6 Hz,

C3, 04, CS); 55.9 (d, J = 84.8 Hz, NQHMe); 45.9 (t, J = 84.5, ngg), 40.2 (q,

28

J = 47.7 Hz, Nfleg); 28.4 (d, J = 42.0 Hz, BCH); 22.3 (q, J = 35.6 Hz, 7 CH3);
21.7 (q, J = 35.5 Hz, YcH3); 11.8 (q, J = 38.8, NCHQH3).
Anal. Calcd. for C13H27FeNS: C, 62,61; H, 7.83.

Found: C, 62.81; H, 7.99.

(§,§)-l-(1-Dimethylaminoethyl)-2-n—butylthiferrocene (33, R = g-Bu)
The procedure was the same as for _S_Q, R = _t_-Bu, except that 0.76 mL
(4.0 mmol) of fl-BUZSZ was used. The product was obtained as brownish orange
oil: yield 81.296.
MS m/e (relative intensity), 345 (91, M“), 330 (31, M+-Me), 302 (11, M+-Pr),
301 (48, M+-NMe2), 300 (51, M+-HNMe2), 256 (5, M+-SBu), 121 (42, FeCp),
65 (6, Cp), 56 (48, Fe), 45 (20, HNMez), 44 (42, NMeg).
IR (neat, C81), 3100 (ring C-H stretch), 2970, 2940, 2860, 2820 (alkyl C-H stretch),
1460 (asymmetric C-H bend), 1380 (symmetric C-H bend), 1265, 1245 (alkyl
C-H bend), 1190 (ON stretch), 1106 (asymmetric ring breathing), 1000 (unsubsti-
tuted Cp ring stretch), 818 (ring C-H bend perpendicular to ring), 532 (asymmetric
ring tilt), 452 cm"1 (asymmetric ring-Fe stretch).
1H NMR( ppm), 4.31 (m, 1H, H3, H4, H5); 4.10 (s, 5H, Cp), 3.97 (q, J = 6.8
Hz, 1H, NCHMe); 2.79 (ddd, Jgem = 13.0 Hz, Jvic = 7.0 Hz, 1H, SCH2); 2.61
(ddd, Jgem = 13.0 Hz, Jvic = 7.0 Hz, 1H, SCHZ); 2.12 (s, 6H, NMeg), 1.51 (m,
2H, 8 CH2); 1.37 (m, 2H, Y CH2); 1.36 (d, J = 6.8 Hz, 3H, NCH§_I_I_3); 0.88 (t,
J = 6.8 Hz, 3H, 6 CH3).
130 NMR (6 ppm), 93.5 (s, CZ); 80.5 (s, CI); 73.5 (d, J = 89.4 Hz, 03, c4, c5); .
69.9 (d, J = 86.4 Hz, Cp); 67.5 (d, J = 86.4 Hz, c3, c4, 05); 66.5 (d, J = 87.5
Hz, 03, c4, cs); 55.9 (d, J = 66.3 Hz, NgHMe); 40.2 (q, J = 49.0 Hz, NMe2);
36.4 (t, J = 56.3 Hz, SCH2); 31.8 (t, J = 38.5 Hz, 8 CH2); 21.9 (t, J = 36.9 Hz,
7 CH2), 13.7 (q, J = 34.0 Hz, 6 CH3); 11.9 (q, J = 39.5 Hz, NCHggg).

Anal. Calcd. for C18H27FeNS: C, 62.61; H, 7.88.

29

Found: C, 62.50, H, 8.00.

(R,§)-l—(1-DimethylaminoethyD—Z-isopentylthioferrocene (_53, R = i—Pent.)

The amine (§)-_7_ (0.5 g, 1.95 mmol) was dissolved in 40 mL dry ether in
a 100 mL round-bottomed schlenk flask equipped with a side arm and a rubber
septum. The suspension was cooled to -78°C and while being stirred 0.8 mL
of 2.8 M fl-BuLi (2.14) mmol) was added dropwise via a syringe. The orange
suspension was allowed to reach room temperature and stirred overnight.
Then 0.41 g isopentyldisulfide (1.99 mmol) dissolved in 30 mL hexane was added
dropwise via cannula to the orange solution at -78°C. The reaction mixture
was allowed to reach room temperature and stirred under N2 for an additional
24 h, after which saturated aqueous NaHCO3 was added to the mixture. The
resulting organic layer and ether extracts from the aqueous layer were combined,
washed with cold water, dried, and evaporated to a brown oil that was chromato-
graphed on a silica gel (hexane/CHZCIZ/EtZO). The product was obtained
as a light brown oil: yield 72%.
MS m/e (relative intensity), 359 (60, M + ), 344 (20, M+-Me), 315 (25, Mt—
NMeg), 314 (32, M+-HNMe2), 121 (10, FeCp), 103 (8, S-Pent), 56 (12, Fe).
1H NMR ( Gppm), 4.31 (m, 1H, H3, H4, H5); 4.20 (m, 1H, H3, H4, H5); 4.16
(m, 1H, H3, H4, H5); 4.10 (s, 5H, Cp); 3.98 (q, J = 7.0 (Hz, 1H, NCHMe); 2.85
(m, 1H, q CH2); 2.63 (m, 1H, aCI-Ig); 2.10 (S, 6H, NMeZ); 1.71 (m, 2H, BCHZ);

1.45 (m, 1H, CH); 1.35 (d, J = 7.0 Hz, 3H, NCHCH3), 0.82-0.90 (dd, 6H, CHMez).

(§,§)-l -(1-Di methylaminoethyl)-2-phenylthioferrocene (g, R = Ph)

The amine (_I_l_)-1(1.5 g, 5.8 mmol) was dissolved in 50 mL dry ether and
placed in a 200 mL round bottomed flask equipped with a side arm and rubber
septum. The suspension was cooled to -40°C and 4.0 mL (6.4 mmol) fl-BuLi
was added slowly via a syringe. the orange suspension was allowed to reach

room temperature and stirred overnight. Ph282 (1.29 g, 5.91 mmol), dissolved

30

in 30 mL warm hexane, was added dropwise via cannula to the orange suspension
at -7 8°C. The resulting solution was allowed to reach room temperature and
then refluxed overnight under N2. Upon cooling the reaction mixture to room
temperature, 30 mL H20 was added. The resulting organic layer was separated,
dried and evaporated to give a dark oily residue. Unreacted Ph282 was removed
by sublimation. The oil was chromatographed on activated alumina by eluting
first with hexane and then with CHZCIZ, to the product, which was recrystallized
from hexane/CH2012 to give orange crystals: yield 85%, mp 70-72°C.

MS m/e (relative intensity), 365 (70, M+), 320 (78, M+-HNMe2), 212 (31, vinylfer-
rocene), 121 (54, FeCp), 72 (100, CHMeNMeg), 56 (45, Fe).

1H NMR (6 ppm) 7.05-7.25 (m, 5H, Ph); 4.53 (m, 1H, H3, H4, H5); 4.42 (m,

1H, H3, H4, H5); 4.30 (m, 1H, H3, H4, H5); 4.18 (s, 5H, Cp); 3.85 (q, J = 7.0

Hz, NCHMe); 1.90 (s, 6H, NMeg); 1.45 (d, J = 7.0 Hz, NCHC_H3).

Anal. Calcd. for CZOH23FeNS: C, 65,75; H, 6.30.

Found: C, 65.32; H, 6.21.

(_1_l_,§)-l-(1-Dimethylaminoethyl)—2-benzylthioferrocene (5_5_, R = CHzPH)

The procedure was the same as for 34, R = Ph, except that 1.45 g (5.88
mmol) of (PhCH2)282 was used. The product was obtained as a brown oil:
yield 75%.

MS m/e (relative intensity), 379 (25, M+), 334 (54, M+-HNMe2), 244 (39), 121
(57, FeCp), 91 (100, CHZPh), 72 (84, CHMeNMez), 56 (54, Fe).

IR (neat), 3090-3000 (ring C-H stretch), 1490 (CH2 scissoring of SCHZ), 1000
(unsubstituted Cp stretch), 456 cm"1 (asymmetric ring-Fe stretch).

1H NMR (6 ppm), 7.18 (m, 5H, Ph); 4.20 (m, 1H, H3, H4, H5; 4.15 (m, 1H, H3,
H4, H5); 4.11 (m, 1H, H4, H5); 4.06 (s, 5H, Cp); 4.0 (q, J = 7.0 Hz, 1H, N_C_IiMe);
3.90 (m, 2H, SCHz); 2.21 (s, 6H, NMeg); 1.38 (d, J = 6.8 Hz, 3H, CH_M_8_).

13c NMR (6 ppm), 138.9 (s); 129.1(d), 128.3(d), 126.7 (d, Ph), 79.3, 74.5, 71.6,

31

69.99 (d, Cp), 67.99, 67.03, 56.4 (d, _(_3_HMe), 41.45 (t, 82112), 39.95 (q, NMeZ),
10.88 (q, CH_M_e_).
Anal. Calcd. for C21H25FeNS: C, 66.49; H, 6.60.

Found: C, 66.52, H, 6.65.

(_I_l_,_S_)-1-(1-DimethylaminoethyD-Z-(p—tolyDthioferrocene (LG, R = p—tonl).

The amine (_R_)—_7_ (0.5 g, 1.95 mmol) was dissolved in 30 mL dry ether and
placed in a 100 mL round—bottomed schlenk flask equipped with a side arm
and rubber septum. The suspension was cooled to -70° C and 0.8 mL (2.14 mmol)
of 2.7 M _t_i-BuLi was added slowly via a syringe. The orange suspension was
allowed to reach room temperature and stirred overnight. Then p-tolyl disulfide
(0.48 g, 1.94 mmol), dissolved in 30 mL warm hexane, was added dropwise
via cannula to the orange suspension at -7 0°C. The reaction mixture was allowed
to reach room temperature and stirred for 12 h under N2. Saturated aqueous
NaHCO3 was added to the mixture and the resulting organic layer and ether
extracts of the aqueous layer were combined. After drying and evaporation
of solvent, the resulting product mixture was chromatographed on a silica
gel column (hexane/CH2C12/ether). The product was obtained as yellow crystals
upon recrystallization from hexane/CHZCIZ: yield 85%, mp 66-67°C.
MS m/e (relative intensity), 379 (81, W), 364 (27, M+-CH3), 335 (52, Ml”—
NMeZ), 334 (19, M+HNMe2), 121 (90, FeCP), 72 (100, CHMeNMez), 56 (55,
Fe).
1H NMR (6 ppm), 7.11—6.94 (m, 4H, 06H4); 4.49 (m, 1H, H3, H4, H5); 4.30
(m, 1H, H3, H4, H5); 4.25 (m, 1H, H3, H4, H5); 4.15 (S, 5H, Cp); 3.86 (q, J =
7.0 Hz, 1H, NCflMe); 2.24 (s, 3H CH3Ph); 1.94 (s, 6H, NMeg), 1.46 (d, J = 7.0
Hz, 3H, NCHCH3).
13C NMR (6 ppm), 138.0 (s, substituted phenyl C); 135.2 (5, para substituted

phenyl C); 129.6 (d, J = 103.0 Hz, phenyl C); 128.2 (d, J = 106.2 Hz, phenyl

32

C); 94.3 (S, C2); 77.9 (5, C1); 76.0 (d, J = 97.0 Hz, C3, C4, C5); 70.9 (d, J =
92.2 Hz, Cp); 69.1 (d, J = 93.2 Hz, C3, C4, C5); 68.7 (d, J = 94.2 Hz, C3, C4,
Cs); 56.6 (d, J = 70.0 Hz, NQHMe); 40.4 (q, J = 50.0 Hz, NMez); 20.9 (q, J =
51.0 Hz, _C_3_H3-Ph); 12.7 (q, J = 43.3 Hz, NCHQH3).

Anal. Calcd. for CZIH25FeNS: C, 66.49; H, 6.60.

Found: C, 66.25; H, 6.82.

(§,_S_)—1-(1-Dimethylaminoethyl)—2-(4-chlorophenyl)thioferrocene (g, R = 4-chloro—
phenyl).

The amine (3)12 (1.0 g, 3.89 mmol) was dissolved in 50 mL dry CHZClg
and placed in a 200 mL round-bottomed schlenk flask equipped with a side
arm and rubber septum. The solution was cooled to —7 0°C and 1.6 mL (4.28
mmol) of 2.7 _N_l n—BuLi was added slowly via a syringe. The orange solution
was allowed to reach room temperature and stirred overnight under N2. Then
4-chlorophenyl disulfide (1.12 g, 3.9 mmol), dissolved in 50 mL dry CHZCIZ,
was added dropwise via cannula to the solution at —70°C. The reaction mixture
was allowed to reach room temperature and stirred for 12 h under N2. Saturated
aqueous N aHCO3 was added and the resulting organic layer and ether extracts
of the aqueous layer were combined. After drying and evaporation of solvent,
the resulting product mixture was chormatographed on a silica gel column
(hexane/ether). The product was obtained as yellowish orange crystals upon
recrystallization from CHZClg/petroleum ether: yield 7 2%, mp 97-98°C.
MS m/e (relative intensity), 399.5 (21, M”), 355 (27, M+-NMe2), 354 (20, M+-HNMe2,
143 (7, S-4-chlorophenyl), 121 (75, FeCp), 72 (100, HCMeNMeg), 56 (55, Fe),
44 (34, NMeg).
IR (KBr pellet), 3100—3050 (ring C-H stretch), 2970, 2930, 2820 (alkyl C-H
stretch), 1575 (phenyl C-C stretch), 1185 (C-N stretch), 1001 (unsubstituted

Cp stretch), 470 cm'1 (asymmetric ring-Fe stretch).

33

1H NMR (6 ppm), 7.12-7.04 (m, 4H, 06114); 4.47-4.25 (m, 3H, H3, H4, H5);
4.17 (S, 5H, Cp), 3.87 (q, J = 7.0 Hz, 1H, NCflMe); 1.92 (S, 6H, NMeg); 1.40

(d, J = 7.0 Hz, 3H, NCHC_I_I_3).

13C NMR (6 ppm), 141.0 (s, substituted phenyl C); 130.5 (s, p-phenyl C); 128.8
(d, J = 105.0 Hz, phenyl C); 128.8 (d, J = 105.3 Hz, phenyl C); 95.0 (3, C2);
76.2 (d, 03, c4, cs); 76.1 (s, 0;); 70.8 (d, J = 90.0 Hz, Cp); 69.4 (d, 03, c4,
C5); 69.0 (d, c3, C4, c5); 56.5 (d, J = 66.0 Hz, N_(_:_H); 39.8 (q, J = 48.5 Hz,

NMez),; 11.0 (q, NCHQHg).

B. Preparation of Metal Complexes
The complexes (_I}_,§)-CsH5Fe(C5H3-1-CHMeNMe2-2-SR)MC12 where R
= Me, i-Pr, n-Pr, i-Bu, Ph, p-tolyl, 4-chlorophenyl; M = Pd, Pt, were prepared
from benzene solutions of the appropriate (PhCN)2MC1279 species and a slight
excess of the ferrocenylsulfide ligand in an approximate 1:1.1 molar ratio.
The reaction mixture was stirred for 10 h in the case of Pd complexes, and
for a week in the case of Pt complexes. The resulting precipitates were filtered,
washed with benzene, then with petroleum ether, and recrystallized from CHZClg/-

hexane by slow evaporation.

Dichloro[(_19-l -(_S_)-2-Methylthioferrocenylethyldi methylaminel-palladium(ll)-
18

Deep purple needles decomposed at 162-164°C.
1H NMR (6 ppm), 4.51 (m. 1H, H3, H4, H5); 4.40 (m, 2H, H3, H4, 115); 4.23
(5, 5H, Cp); 3.87 (q, J = 6.8 Hz, 1H, NCHMe); 3.21 (S, 3H NMez); 2.70 (S, 3H,
SMe); 2.31 (s, 3H, NMez); 1.55 (d, 3H, NCHCfl3).
MS m/e (relative intensity), 303 (2, M+-PdClg), 258 (100, M+-PdClz-HNMe2),
121 (34, FeCp), 56 (16, Fe).

Anal. Calcd. for C15H21FeNSPdC12: C, 37.47; H, 4.37.

34
Found: C, 36.43; H, 4.31.

Dichloro[(_R)-1 -(§)-2-isopropy1thioferrocenylethyldimethylaminel-palladium(Il)-5_9_.
Deep brown crystals decomposed at 151-153°C.

1H NMR (6 ppm), 4.63 (m, 1H, H3, H4, H5); 4.48 (m, 2H, H3, H4, H5); 4.27

(s, 5H, Cp); 3.88 (m, 1H, SCflMez); 3.80 (q, J = 7.0 Hz, 1H, NCflMe); 3.17 (s,

3H, NMez), 2.24 (s, 3H, NMeg); 1.93 (d, J = 7.0 Hz, NCHC_I_l_3); 1.75 (d, J =

7.0 Hz, 3H, 8CH3); 1.53 (d, J = 7.0 Hz, 3H, 8CH3).

IR (KBr pellet), 493 (b), 460 (Sh, Pd-N stretch), 320 (b, Pd—Cl or Pd-S stretch);

300 cm’1 (b, Pd-Cl or Pd—S stretch).

Anal. Calcd. for CI7H25FeNSPdC12: C, 40.15, H, 4.95.

Found: C, 39.90; H, 4.19.

Dichlor[(R)-l-(_S_)-2-propylthioferrocenylethyldimethylaminel-palladiumaD-(jfl
Deep brown crystals decomposed at 162-164°C.

1H NMR (6 ppm), 4.49 (m, 1H, H3, H4, H5); 4.40 (m, 2H, H3, H4, H5); 4.21

(s, 5H, Cp); 3.86 (q, J = 6.8 Hz, 1H, NCHMe); 3.57 (m, 1H, SCHZ); 3.05 (m,

1H, SCHz); 3.19 (s, 3H, NMez); 2.30 (8, 3H, NMez); 2.24 (m, 1H, CH2); 2.03

(m, 1H, 8 CH2); 1.52 (d, J = 6.8 Hz, 3H, NCHC_I_{_3); 1.17 (t, J = 7.0 Hz, 3H,

Y CH3).

IR (KBr pellet), 465 (sh, Pd-N stretch), 322 cm“1 (b, Pd-Cl or Pd-S stretch).

Dichloro[(§)-1-(_S_)-2—isobutylthioferrocenyl ethyldi methylaminel—palladiu mm)-
31.

Dark brown crystals decomposed at 144-145°C.
1H NMR (6 ppm), 4.44 (m, 1H, H3, H4, H5); 4.39 (m, 2H, H3, H4, H5); 4.21
(s, 5H, Cp); 3.83 (q, J = 7.0 Hz, 1H, NCflMe); 3.67 (d, 1H, SCH2); 3.19 (s, 3H,
NMeg); 2.82 (d, 1H, SCHZ); 2.37 (m, 1H, 8 CH); 2.33 (s, 3H, NMeZ); 1.52 (d,
J = 7.0 Hz, 3H, NCHC_I-I3); 1.20 (d, J = 7.0 Hz, 3H, Y CH3); 1.18 (d, J = 7.0

Hz, 3H, YCH3).

35

13c NMR (6 ppm), 80.2 (s, C2); 71.0 (d, C3, C4, C5); 68.2 ((1, C3, C4, C5);

67.8 (d, C3, C4, C5); 64.5 (s, C1); 63.2 (d, NCH); 50.1 (t, SCHZ); 50.1 (q, NMez);
41.0 (q, NMeZ); 27.5 (d); 22.3 (q, Y CH3); 21.4 (q, YCH3); 10 (q, NCH9H3).
Anal. Calcd. for C18H27FeNSPdC12: C, 41.37; H, 5.21.

Found: C, 41.10; H, 5.15.

Dichloro[(_R)-l-(§)-2—phenylthioferrocenylethyldimethylamine]—palladium(II)-—
_6_2.
Greenish black crystals decomposed at 165-166°C.
1H NMR (6 ppm), 8.00—7.50 (m, 5H, C6H5); 4.36 (m, 1H, H3, H4, H5); 4.25
(m, 1H, H3, H4, H5); 4.10 (s, 5H, Cp); 4.03 (q, J = 6.8 Hz, 1H, HCHMe); 4.02
(m, 1H, H3, H4, H5); 3.28 (s, 3H, NMeg); 2.36 (s, 3H, NMez); 1.52 (d, J = 6.8
Hz, 3H, NCHCH3).
IR (KBr pellet), 482 (sh), 443, 323 (b, Pd-Cl or Pd-S stretch), 298 cm-1 (s, Pd-Cl
or Pd-S stretch).
Anal. Calcd. for C20H23FeNSPdC12: C, 44.25; H, 4.24.

Found: C, 44.18, H, 3.96.

Dichloro[(_l_t)—1—(_§)-2-paratolythioferrocenylethyldimethylaminel—palladium(II)-
33.

Dark brown needles decomposed at 158-159°C.
1H NMR (6 ppm), 7.80-7.28 (m, 4H, C5H4); 4.33 (m, 1H, H3, H4, H5); 4.21
(m, 2H, H3, H4, H5); 4.00 (s, 5H, Cp); 3.96 (q, J = 7.0 Hz, 1H, NCHCH3); 3.16
(s, 3H, NMeg); 2.36 (s, 3H, para CH3); 2.22 (s, 3H, NMez); 1.44 (d, J = 7.0 Hz,
3H, NCHC_H_3).
IR (Nujol) 550, 500 (b, asymmetric ring tilt), 460 (sh, Pd-N stretch), 330 (sh,

Pd-Cl or Pd-S stretch), 297 cm-1 (m, Pd-Cl or Pd-S stretch).

36

Dichloro[(_R)—1-(_S_)-2-(4-chlorophenyl)thioferrocenylethyl-dimethylaminelpal-
ladium(II)-_6_4_.

Greenish brown powder decomposed at 198-200°C.
1H NMR (6 ppm), 8.04-7.55 (m, 4H, 06H4); 4.68 (m, 1H, C3, C4, C5); 4.50
(m, 2H, C3, C4, C5); 4.21 (q, J = 6.8 Hz, 1H, NCHMe); 4.12 (s, 5H, Cp); 3.18

(5, 3H, NMeg); 2.24 (S, 3H, NMez); 1.50 (d, J = 7.0 Hz, 3H, NCHCM3).

Dichloro[(§_)—l-(_S_)-2—(4—chlorophenyDthioferrocenylethyldi methylaminelpla-
tinum(II)-6__5.
Yellow flakes decomposed at 218-220°C.
1H NMR (6 ppm), 7.40-7.22 (m, 4H, C6H4); 4.5-4.2 (m, 3H, H3, H4, H5); 4.13
(s, 5H, Cp); 3.88 (q, 1H, NCMMe); 3.18 (s, 3H, NMeg); 2.25 (s, 3H, NMez); 1.45
(d, 3H, NCHMe).
IR (KBr pellet), 4.58 (sh, Pt-N), 336 cm‘1 (sh, Pt-Cl or Pt-S), 320 cm-1 (W,Pt-Cl).
Anal. Calcd. for C20H22FeNSPtCl3: C, 36.06; H, 3.31.

Found: C, 36.29; H, 4.22.

(_R,§_)—1-(l-Dimethylaminoethyl)-2-(dimethyldithiocarbamatehferrocendfi).

A 2.7 M solution n—BuLi in hexane (1.6 mL, 4.3 mmol) was slowly added
via a syringe to a solution of (§)-1-(dimethylamino)-ethylferrocene (1.0 g,
3.9 mmol) in 50 mL dry diethyl ether at -78°C. The solution was allowed to
reach room temperature and stirred for an additional 12 h water N 2. Tetramethyl—
thiuram disulfide (0.94 g, 3.9 mmol) in 60 mL of benzene was added via cannula
to the orange solution that had been cooled to -7 8°C. The solution was allowed
to reach room temperature and was stirred overnight, and then 40 mL saturated
aqueous NaHCO3 added to the dark brown solution. The resulting organic
layer and ether extracts from the aqueous layer were combined, washed with
cold water and dried over anhydrous N aZSO4. Evaporation of the solvent gave

a dark brown product mixture that was chromatographed on a silica gel column

37

(hexane/benzene/ether/methanol). The product was recrystallized from CH2012/-
hexane to give yellowish orange crystals: yield 82.296, mp 103-105°C.

MS m/e (relative intensity), 376 (61,M+), 311 (33, M+—Cp), 287 (20), 256 (100,
M+-8C8NMe2), 255 (19, M+-Fecp), 241 (93, M+-SCSNMe2-Me), 121 (3, FeCp),
88 (52, CSNMez), 72 (11, CHMeNMez).

IR (KBr pellet), 2980, 2940, 2780, 1495 cm-1.

1H NMR (6 ppm) at 22°C; 4.63 (dd, 1H, H3, H5); 4.46 (t, 1H, H4); 4.40 (dd,

1H, H3, H4); 4.15 (s, 5H, Cp); 3.71 (q, J = 7.0 Hz, 1H, NCMMe); 3.50 (s, 6H,
NMeg); 2.10 (s, 6H, NMez); 1.52 (d, J = 7.0 Hz, 3H, NCHC_i_i_3).

13C NMR (6 ppm) at 27°C; 198.9 (s, CS); 91.7 (s, C1), 76.2 (d, C3, C4, C5);

74.9 (s, C2), 69.9 (s, Cp); 69.6 ((1, C3, C4, C5) 68.6 (d); 68.4 (s); 55.6 (t, N_C_3_HMe);
40.8 (q, NMeg), 18.0 (q, NCHgHg).

Anal. Calcd. for C17H24FeN282: C, 54.25; H, 6.38.

Found: C, 53.62; H, 6.63.

(_1_l_,_8_)-1-(1-Dimethylaminoethyl)-2-(diethyldithiocarbamate)-ferrocendfl ).

A 2.5 Msolution M-BULI in, hexane (1.0 mL, 2.57 mmol), was slowly added
via a syringe to a solution of (§)-1-(dimethylamino)—ethylferrocene (0.65 g,
2.57 mmol) in 30 mL dry diethyl ether at -7 8°C. The solution was allowed
to reach room temperature and stirred for an additional 12 h under N2. the
solution was then cooled to -78°C and tetraethylthiuram disulfide (0.8 g, 2.7
mmol) in 35 mL toluene was added. The solution was stirred overnight at room
temperature and 30 mL saturated aqueous NaHCO3 added. The resulting organic
layer and ether extracts from the aqueous layer were combined, washed with
cold water and dried. Evaporation of the solvent gave a brown product mixture
that was chromatographed on a silica gel column (hexane/benzene/ether/methanol).
The product was recrystallized from CHZCl/hexane to give brown crystals,

mp 82-85°C.

38

MS m/e (relative intensity), 404 (2, M+) 297 (16), 213 (11), 148, (12, SCSNEtg),
116 (100, CSNEtz), 72 (2, NEt2).

IR (KBr Nujol) 1498 cm‘l.

1H NMR (6 ppm) at 27°C, 4.60 (dd, 1H, H3, H5); 4.48 (t, 1H, H4); 4.40 (dd,
1H, H3, H5); 4.12 (s, 5H, Cp); 3.96 (q, J = 7.0 Hz, 2H, CMZCH3); 3.82 (q, J

= 7.0 Hz, 2H, CMZCH3); 3.63 (q, J = 7.0 Hz, 1H, NCMMe); 2.15 (s, 6H, NMeg);
1.46 (d, 3H, NCHC_H_3); 1.3-1.42 (tt, 6H, carbamate CH3).

130 NMR (6 ppm); 197.3 (s, cs); 86.6 (s, C1); 86.5; 77.5; 76.5, 68.6 (d, Cp);
67.8 (C3, C4, C5); 67.4 (d, NQHMe); 66.6; 66.4; 57.9; 51.0 (t, NCHZ); 46.8 (t,
carbamate CH2); 39.9; 15.2 (q, NCHQH3); 12.9 (q, carbamate CH3); 10.0 (q,

carbamate CH3).

C. Catalytic Applications of Compler

(i) Asymmetric Grignard Cross—Couplllg Reactions

The cross-coupling reactions were carried out in essentially the same
manner as was previously reported.67 Since the optical rotation of the coupling
product (4-phenyl-1-pentene) was strongly affected by small impurities,70
in addition racemization of products always occurred, it was difficult to determine
the optical purity of the product by use of polarimeter. The alkene was thus
converted into the methyl ester, of which the enantiomeric purity was determined
by 1H NMR spectroscopy in the presence of a chiral shift reagent, Eu(dcm)3.82
Detailed procedures for cross—coupling reactions and conversion of 4-phenyl-1--

pentene to methyl 3-phenyl-butyrate follow.

Grignard cross-coupling reaction of allylmagnesium chloride to 4—phenyl-1—
pentene usirg complex 5_8_, _5_9_, §_2_, _63, or £4.
The catalyst (0.0499 mmol) was placed in a 100 mL round-bottomed schlenk

flask equipped with a stirring bar and a septum. The vessel was evacuated

39

and filled with'Ar several times. After being cooled to -78°C, the reaction
vessel was charged with 1.41 g (10.0 mmol) l—phenylethyl chloride in 20 mL

dry ether and stirred for 2 h at room temperature before addition of allylmagnesium
chloride (20 mmol, 10 mL of a 2 M solution in THF) via syringe at -78°C.

The reaction mixture was allowed to warm to 0°, stirred for 40 h, and hydrolyzed
with 1096 HCl. The organic layer and ether extracts from the aqueous layer
were combined, washed with saturated NaHCO3 solution and water, and dried
over NaZSO4. Evaporation of solvent and chromatography on a silica gel column
(hexane/CHZCIZ) gave 93 to 98.5% of 4-phenyl-1-pentene.

1H NMR (6 ppm) 1.25 (d, 3H, CH3), 2.35 (m, 2H, CH3), 2.80 (m, 1H, CMCH3),
5.00 (m, 2H, CH=CM2), 5.70 (m, 1H, C_H_=CH2), 7.25 (m, 5H, Ph); Lit.83 1H

NMR( ppm) 1.24 (d, 3H, CH3), 2.32 (m, 2H, CH2), 2.75 (sex, 1H, CMCH3),

4.80 (s, 1H, CH=_(_3_H2), 4.92 (split d, 1H, CH=CH2), 5.52 (m, 1H, CM—CHZ),

7.0 (5H, Ph); MS m/e (relative intensity), 41 (5, CHZCH=CH2), 77 (15, C6H5),

105 (100, PhCHCH3), 146 (15, M+). Results are shown in Table 20.

Conversion of 4-phenyl-l -pentene to methyl 3—phenylbutyrate

The reported precedure84 for oxidation of 3—phenyl-1-butene was followed.
To a solution of 4—phenyl-1-pentene (0.453 g, 3.1 mmol) in 80 mL te_rt-butyl
alcohol were added a solution of 1.24 g (9.0 mmol) K2CO3 in 60 mL of water
and a solution of 5.13 g (24 mmol) of sodium periodate and 0.63 g (4.0 mmol)
of KMnO4 in 60 mL of water. The solution was adjusted to pH 8.5 with 2N
aqueous NaOH and was stirred overnight. After _th-butyl alcohol was removed
under reduced pressure, the aqueous. solution was acidified with concentrated
HCl to pH 2.5, and sodium bisulfite was added until the solution became off-white.
The solution was extracted with ether and the extracts were dried over Na2SO4,
concentrated and distilled [120-135°C (2mm)]. A solution of the acid thus

obtained (0.295 g, 128 mmol) and p-toulenesulfonic acid (40 mg) in 10 mL of

40

methanol was refluxed for 3 h. The solvent was removed under reduced pressure,
and the residue was taken up in ether. The solution was washed with 10%
aqueous sodium hydroxide dried over anhydrous N82504, and evaporated.

The residue was distilled [110-130°C (2mm)] to give about 72-85% of methyl
3-phenyl—butyrate; 1H NMR (6 ppm), 1.29 (d, J = 7.0 Hz, 3H, CHC_H_3), 2.53

(dd, Jgem = 15 Hz, Jvic = 8 Hz, 1H, CMZCH), 2.63 (dd, Jgem = 15 Hz, Jvic

= 8 Hz, 1H, CMZCH), 3.28 (sex, J = 7.0 Hz, 1H, CH2CMPhMe), 3.61 (s, 3H,
OCH3), 7.16-7.45 (m, 5H, “Ph). 1H NMR spectroscopy with the chiral shift
reagent Eu(dcm)3 showed varying enantiomeric excess (e.e) values as the catalyst

was varied (results in Table 20).

(ii) Selective Hydrogenation of Conjugated Dienes to Alkenes with _5_8_,
922.5.-
In all the cases studied, a period of induction was observed except when

additives were introduced. The induction time was dependent on the catalyst.

Hydrogenation of 1,3-cyclooctadiene with _5_8_, gig-94 in acetone at 67 psi.

The complex (2.0 x 10‘5 mol), acetone (9.0 mL) and 1,3 cyclooctadiene
(0.91 mL, 7.45 x 10'3 mol) were added to a 100 mL pressure bottle with a pressure
gauge and stirring bar. The bottle was evacuated and filled several times
with H2 to a pressure of 67 psi. After an induction period, uptake of H2 began
and slowed after absorption of about 5.5 x 10"3 mol of H2. The initial turnover
rate, product analysis at the end of reaction, and the calculated selectivity

are shown in Table 17.

Solvent Effects on Hydrogenation of 1 ,3—Cyclohexadiene at Room Temperature
The complex (2.0 x 10'5 mol), 1,3-cyclohexadiene (7.45 x 10‘3 mol) and

9.0 mL of various solvents (acetone, CCl4/acetone, 2:1 and 1:1, and CCl4)

41

were added to a 100 mL pressure bottle with a pressure gauge and stirring
bar. The bottle was evacuated and filled several times with H2 to a predetermined
pressure. The hydrogenation was dependent on the chosen solvent. Results

are shown in Table 18.

X-ray Structure Determination of dichloro[(_R_-1 -(§)-2—Methylthioferrocenylethyl-
dimethylamine]palladium(II)-_5_8_.

Data Collection

A deep purpule pyramidal crystal of dichloro[(§)-1-(_S_)-2-Methylthioferrocenyl-
ethyldimethylamine]palladium(II), 015H21C12FePdNS, having approximate
dimensions of 0.20 x 0.25 x 0.45 mm, was mounted in a glass capillary in a
random orientation. Preliminary examination and data collection were performed
with MoKa radiation ( A = 0.71073 A) on a Nicolet P3F computer controlled
4-circle diffractometer equipped with a graphite crystal incident beam monochro-
mator.

Cell constants and an orientation matrix for data collection were obtained
from least-squares refinement, using the setting angles of 20 reflections in
the range 35 < 2 e < 30°. The orthorhombic cell parameters and calculated
volume are: a = 9.226(3), b = 12.219(4), c = 15.448(5) A, V = 1741.5(8) A3.
For Z = 4 and F.W. = 480.56 the calculated density is 1.83 g/cm3. From the

systematic absences of:

h00 h = 2n+1
0k0 k = 2n+1
001 1 = 2n+1

and from subsequent least-squares refinement, the space group was determined
to be P212121 (# 19).
The data were collected at a temperature of 23(1)°C using the 2theta-theta

scan technique. The scan rate varied from 4 to 30 °/ min (in 2 9 ). The variable

42

scan rate allows rapid data collection for intense reflections where a fast
scan rate is used and assures good counting statistics for weak reflections
where a slow scan rate is used. Data were collected to a maximum 2 e of
60°. The scan range (in deg.) was determined as a function of 2 6 to correct

for the separation of the KO, doubletl; the scan width was calculated as follows:
2 9 scan width = 2.00 (26 (K0, 2) - (29 (K o 1))

The ratio of peak counting time to background counting time was 1:1. The
diameter of the incident beam collimator was 1.0 mm and the crystal to detector

distance was 19 cm.

Data Reduction

A total of 2937 reflections were collected, of which 2912 were unique
and not systematically absent. As a check on crystal and electronic stability
3 representative reflections were measured every 45 reflections. The slope
of the least-squares line through a plot of intensity versus time was -17(16)
counts/hour which correspondsto a total loss in intensity of 0.3%. A linear
decay correction was applied with correction factors on I ranging from 1.000
to 1.003 and with an average value of 1.002.

Lorentz and polarization corrections were applied to the data. The linear
absorption coefficient is 22.7 cm‘1 for Mo KO, radiation. An empirical absorption
correction based on a series of psi-scans was applied to the data. Relative
transmission coefficients ranged from 0.892 to 0.999 with an average value
of 0.959. A secondary extinction correction was applied.128 The final coefficient,

refined in least-squares, was -0.344 x 10"8 (in absolute units).

Structure Solution and Refinement

The structure was solved using the Patterson heavy-atom method which

43

revealed the position of the Pd atom. The remaining atoms were located in
succeeding difference Fourier syntheses. Hydrogen atoms were located and
their positions and isotropic thermal parameters were refined.

Scattering factors were taken from Cromer and Waber.129 Anomalous
dispersion effects were included in Fc;130 the values for Af' and A f" were
those of Cromer.1 Only the 2175 reflections having intensities greater than
3.0 times their standard deviation were used in the refinements. The final
cycle of refinement included 275 variable parameters and converged (largest
parameter shift was 0.25 times ) with unweighted and weighted agreement

factors of:

R1=2||Fo|-| Fcll /2| Fo|=0.029

R2=SQRT(X w ( |Fo|-| Fc|)2/z w F02) = 0.029

The standard deviation of an observation of unit weight was 1.29. The standard
deviation of an observation of unit weight was 1.29. The highest peak in the
final difference Fourier had a height of 0.59 e/A3 with an estimated error
based on o F of 0.09.131 Plots of 2w( |Fo| - |Fc| )2 versus | F0 | , reflection
order in data collection, sin 6/1 , and various classes of indices showed no
unusual trends.

All calculations were performed on a VAX-11 computer using SDP-PLUS.132

III. RESULTS AND DISCUSSION

RESULTS AND DISCUSSION

A. (MmsHsFeC5H3ICH(CH3)N(CH3)2HSRI
(R = Me, Et, i-Pr, _n-Pr, n—Bu, i-Bu, g-Bu, Ph, CHZPh, i-Pent, p-toly, 4-CI-Ph
There has been considerable interest in chiral ferrocenylphosphine ligands
that possess planar chirality due to a 1,2-unsymmetrically substituted cyclopen-
tadienyl ring and are highly effective as ligands in transition metal catalyzed
asymmetric synthesis.85986 Though few sulfide complexes have been used
as ligands in catalysis, the preparation of several chiral ferrocenylsulfide com—
plexes was undertaken so that possible catalytic applications to hydrogenation
and asymmetric synthesis could be investigated.
Earlier results53 obtained in the syntheses of ferrocenyiamine sulfides
in our laboratory revealed poor yields (from 01.1% yield for phenyl derivative
to 45% yield for ethyl derivative) and products were obtained as yellow powders,
suggesting that products may be salts of the amine and not free ligands. To
circumvent this problem, it was observed that it is necessary to deprotonate
the product by washing with aqueous NaHCO3 prior to final separation. This
has eventually resulted in high yeilds in this work. Nesmeyanov has also reported
that quaternary ammonium salts of the general formula [C5H5FeC5H4CH2N(CH3)2-
CH2R1X", were prepared in high yields by the action of the corresponding
alkyl halides on (dimethylamino-methyl)ferrocene even at low temperature.87:88
This factor will decrease the yield of the chiral ferrocenyl tertiary amine
thioethers. To avoid the problem, we have consistently used dry ether as the
solvent in the synthesis and not halogenated organic solvents (CHZClg, CHCl3,

CC14), even though the starting material is highly soluble in such solvents.

44

45

1. Preparation

A number of previously unknown chiral ferrocenylamine thioether ligands
of the type (_11,§_)-C5H5FeC5H3[CH(CH3)N(CH3)2][SR] where R = Me, Et,_i_-Pr,
_n-Pr, fl-Bu, _i_-Bu, .t_-Bu, _i_-Pent, Ph, CHZPh, p-toyl, 4—Cl-Ph, have been prepared
in a general, high yield, one step synthesis shown in scheme 13. The starting
material (_R)—N,N—dimethyl-l-ferrocenyl ethylamine [(_I}_)-_7_] was prepared from
ferrocene according to Ugi's procedure77 and was resolved by using (§)-(+)-tartaric
acid. As illustrated by Ugi,33 the (BO-amine [(5)4], is stereoselectively lithiated
by fl-butyllithium to give 96% of the (PM-(3)1. The (EU-(B) derivative is thought
to be stabilized by the coordination of the adjacent nitrogen atom (in the side
chain) to the lithium atom. The lithiated chiral ferrocene derivative is then
treated with the appropriate disulfides to produce the product as (§)-(§_)-amines.
In some cases (like in preparation of the phenyl derivative), it may be necessary
to reflux the reaction mixture before work-up. The chiral ferrocenyl-amine
sulfide products (iii-_S_?) are usually deprotonated by washing with aqueous
NaHCO3 before separation by chromatography on alumina or silica gel column.
It should be noted here that the chiral ferrocenylamine sulfide compounds
M5351 contain two elements of chirality. The (R) configuration refers to the
asymmetric carbon while the (§) configuration refers to the planar chirality.
The yields of these products are fairly high (ranging from 45% yield in the
ethyl derivative to 85% yield in the p-tolyl derivative) basically due to the
modified procedure adopted in this work.87 The (§)-N,N-dimethyl-1-[(3)-2-lithio-
ferrocenyl]ethylamine, [(§)-(§)-_7_], was not isolated here but rather was prepared

fresh for each reaction.

2. 1H NMR

The 250 MHz 1H NMR data for the chiral ferrocenylamine thioethers

46

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50

ligands (fi-fl) are given in Table 2. The 1H NMR spectra of these compounds
are typical of 1,2—unsym metrically disubstituted ferrocenes in which one of
the rings is unsubstituted. Rosenblum and Woodward89 have shown that there
is free rotation about the Fe-Cp axis in ferrocenes. The barrier to rotation
in ferrocene is only about one-third that of the 2 methyl groups in ethane.90
Consequently, the unsubstituted C5H5 ring appears as a singlet at 4.06-4.17
ppm region (see figures 1-4). Another striking feature of these spectra is the
diastereotopic nature of the S-CHZ protons. The 2 methylene protons appear
at different positions with their appropriate multiplicity. Their splitting pattern
is given in diagramatic form in Figure 5. In the case of the isopentyl derivative,
(fi,§)—_5_§ (Figure 3), the total number of peaks expected from the methylene
protons should be 2(23) = 16. However, the actual number observed was 15
due to overlap of the central peaks.

The upfield peaks (1.90—2.12 ppm) of NMez in these compounds are due
to the ring current effect. The inversion of the pyramidal N of NMez is faster
than the NMR time scale at room temperature, so the nitrogen methyls appear
as singlet in these compounds. Assignments of the disubstituted ring protons
H3, H4, and H5 cannot be made with absolute certainty, since a number of
1H NMR studies91“93 have shown that a single substituent may deshield or
shield positions 3 and 4, in any combination relative to ferrocene. However,
tentative assignments for H3, H4, and H5 have been given in Table 2 and deutera-
tion studies may be necessary to make unambiguous assignments.

The 250 MHz 1H NMR (§-§)-_5_§, R = CHZPh is given in Figure 1. One
point is striking here. The benzylic protons, although diastereotopic, this property
was not observed in the 1H NMR spectra because, the resonance due to the
benzylic protons is partially obscurred probably, by a combination of the cyclo-

pentadienyl and phenyl ring protons. In contrast, the diastereotopic nature

51

 

 

 

 

 

 

JL M.

11111lLLlllllllllllllLllllllLLlljllLlllllllllllllLllLlLlJllllLll‘lllLLLLlllJllllllllilLllll

8 7 5 5 4 3 2 1 0

1

Figure l. 250 MHz H NMR spectrum of §§_, R - CH Ph.

2

52

 

 

 

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ill]HlWTIllIITTITTTTTIWWTIIIIIIIIIITTIII‘IHUIllTiTlllllllTllIIIIIIIIIITTTTTTWIIII[THTIT

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Figure 2. 250 MHz ‘H NMR spectrum of _5_7_, R =- 4-Cl-Ph.

53

 

 

 

 

 

 

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2.60

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2 protons in 53, R =

Splitting pattern of SCH

i-pentyl.

Figureji

56

(BI-(§)"!§

Figure SB: The Chemical Shifts of Substituted Ring Protons (H3, H4, H5) In

(EFZ and (fi,§)—5_§

57

of the methylene protons in the ethyl derivative, (_11-§)-fl, were observed as
two distinct quartets at 2.60 and 2.7 5 ppm. The methyl protons of the sulfide
link gave an upfield triplet signal at 1.15 ppm as expected, while the methyl
protons at the chiral carbon appeared as a doublet at 1.35 ppm. The appearance
of a singlet peak at 4.10 ppm confirmed the presence of an unsubstituted cyclo-
pentadienyl ring, while the multiplet peaks at 4.20 ppm accounted for the

disubstituted Cp ring.

3. 13c NMR

13C N MR is a sensitive tool for measuring the electron density distribution
on the cyclopentadienyl ring in ferrocene.42 Substituents on the ring induce
screening of the nuclei in two different ways, one being due to the magnetic
anisotropy of the substituent and the second to the electronic effect of the
substitutent that consists of both resonance and inductive components.

The 13C NMR data for the chiral ferrocenylamine thio ether ligands (iii-fl)
are presented in Table 3. Koridze94 has assigned the signals in methoxyferrocene
on the basis of deuterium labelling studies. Since such labelling studies were
not carried out in this work, most of the assignments here could be considered
as tentative. However, the assignment of Cl and C2 in the 1,2-disubstituted
cyclopentadienyl ring appear reasonable. C2 reflects the inductive and field
effects of the substituents (~SR) and exhibits the widest range of values of
any of the ring carbons. The C2 resonance in (fi,§)—§§ (i.e. p-tolyl derivative)
is shifted downfield by 26.1 ppm, relative to ferrocene (68.2 ppm“), whereas
the 4-chlorophenyl derivative, (_11,§_)—§I_, is deshielded by 24.9 ppm. the assignments
of C1 and the unsubstituted cyclopentadienyl ring are reasonable, but assignments
of C3, C4 and C5 are more difficult. In addition, it is incorrect to extrapolate

13C data to 1H data. In some cases the chemical shift ordering is the same,

58

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it iii , JWL‘JL‘

l I 1 L
_LLJ‘ LL'L'ALLLLL‘LLILL'l; l LILLL‘ I '- LiL‘lLLLvLLLLLLLL' LLL'IIL'L Li

8 7 6 S 4

I
LLILLLLLI.

1

Figure 6. 250 MHz H NMR spectrum of §§_, R = p-tolyl.

 

61

 

 

 

 

 

 

 

 

W“ JLL‘Jl _AA- *‘JLAWtf‘jv— :7...;_~: _n. 11‘:

J l J L J I L l i l A _J
12am 92.2: mm 5.2a sac 18.8
PPM

13

Figure 7. Gated decoupled C NMR spectrun of §_7_,

62

 

 

 

 

 

 

 

 

 

 

@ALAAAALAALA[AALALLAAglLAAALALALAA‘AALLA.AlAAAALALLAIAAHLAAAALAAAALLLL‘LLLAALAALAL‘ALALAALALAAAILAJA‘AAAALAAALQHAAJA.LA

Figure 8. Gated decoupled ”(2 MR spectrum of i6,

63

but in ferrocenylaldehyde, for example, the carbon order is C3 > C2,95 while

the proton order is H2 > H3.91‘93a 96: 97.

4. Infrared (IR) SpeCtra

As reported by Rosenblum,2 the two most important peaks in the infrared
spectra of ferrocenederivatives, in which one ring is unsubstituted, appear
around 1000 and 1100 cm‘l. In all the chiral ferrocenylamine thioether ligands
(fl-Sl), peaks were observed in this region, thus confirming substitution in
one ferrocenyl ring of these compounds. The IR data are shown in the experimen-
tal section. A general inspection of the IR data indicates that certain frequencies
are common to all the chiral ferrocenylamine thioether compounds (fl-fl).
These frequencies have been tentatively assigned by comparison with the vibrational
spectra of ferrocene2 and dimethylferrocenefi’8

The high frequency infrared bands at 3100-2860 cm‘1 are assigned to
C-H stretching frequencies. The strong absorption around 1450-1380 cm'1
may be associated with alkyl C-H bend whereas the strong absorption at 1100-1050
cm“1 could be assigned to ring breathing modes. The broad band absorptions
in the region of 500-450 cm'1 may be associated with ring-metal vibrations
such as an asymmetric ring-metal tilt and an asymmetric ring—metal stretch.

The mass spectral data (shown in the experimental section) reveal some
important fragments such as M+, FeCp, C5H5, HCMeNMeZ, vinylferrocene
and M+-SR. In addition to these fragments, peaks consistent with the less
abundant isotopes 54Fe, 57Fe, and 34S were observed.

Cullen57’99 has determined the crystal structure of [(PPFA)Rh(NBD)]PF6,
where PPFA is (fi,_S_)-1-(2-di-phenylphosphinoferrocenyl)ethyldimethylamine;

NBD is norbornadiene, and concluded that the chiral ferrocenyl phosphine

64

ligand coordinated to rhodium through both the phosphorous and nitrogen atoms.
Since there is much interest in ligands which have both "hard" and "soft" properties,
investigation of the chelation of the chiral ferrocenylamine sulfide, (fi-fl)

with transition metals, such as palladium and platinum, forms the basis of

interest in this work. In addition, the effectiveness of these chiral ligands

in transition metal catalyzed asymmetric synthesis has been explored.

B. Palladium Complexes of (_l}_,§)-C5H5Fe05F3[CHMeNMeZISR] (R = Me,
_i_-Pr, n—Pr, _i_-Bu, Ph, p—tolyl, 4-Cl—Ph) and Platinum Complexes of (§-_S_)-C5H5Fe05H3—

[CHMeN Me218-4-Cl—Ph]

1. Preparation

Palladium and platinum complexes, (_5_8-§_5_), were made by allowing a benzene
solution of the chiral ferrocenylamine sulfides, (fig, g_8_, fig, _5_1_, _5_1, _5_§_, 331),
to react with bis(benzonitrile) adducts of palladium and platinum chloride
salts (Scheme 14). The heterobimetallic complexes are insoluble in benzene:
the chiral palladium ferrocenylamine sulfide complexes precipitated immediately
while the platinum analog precipitated after being stirred for 8 days.

The palladium complexes are soluble in acetone, methylene chloride and
chloroform, except the phenyl and tolyl derivatives which were only slightly
soluble in these solvents. The platinum complex (51) is also soluble in these
solvents. Analytically pure samples were obtained by the slow evaporation
of the mixed solvent system, methylene chloride-petroleum ether.

Dichloro[(_11)-1-(_S_)‘2-methylthioferrocenylethyldimethyl-amine]palladium(1l),
(18), gave the best crystals as reflected in the elemental analysis and x-ray

crystal structure.

65

s" W

~13, «9
Me 1:0
thmz [PhCN12MC12 F. 5" \c'
Fe Benzene ’ ©
R = Me,

M=p¢

m I

 

(3.9-Ligands

EPI‘,

E—Ph

Sche me 14 i-Bu

— ,

Ph,
p—tOlyl’
4-Cl--Ph

M = Pt, R = 4431’?”

66

o «... « ««.« o 3... « «... E 3.. E 2...

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. 23..

67

2. 1H NMR

250 MHz 1H NMR data for the chiral palladium and platinum complexes,
(18:65), are presented in Table 4. The chiral ferrocenylamine thioether ligand
undergoes a significant change in the 1H NMR spectra upon complexing with
platinum or palladium chlorides. Figure 9 indicates that the most striking
difference in the 1H NMR spectra of the complexed ligand relative to the
free ligand is the large downfield shift of the resonance due to H3, H4 and
H5 of the substituted cyclopentadienyl ring. This deshielding effect was originally
thought to be due to a severe tilting of the cyclopentadienyl rings where H 3,
H4 and H5 were further from the shielding iron atom.100 The crystal structure
of the chiral methylthioether palladium complex (fl), (discussed in detail in
a later section) however, indicated that the cyclopentadienyl ring was tilted
3.2° from the plane. The large downfield shift of H3, H4 and H5 is either
due to the magnetic anisotropy or the inductive effect of the metal chloride.
A further difference between the 1H N MR spectra of the free ligand and complexed
methyl ligand is the deshielding of the alkyl protons. In particular, the resonance
due to sulfur methyl protons shifts from 2.30 to 2.70 ppm.

Sokolov had observed that the chemical shifts of two methyl groups in
N M62 of a 2-dimethylaminomethylferrocenyl palladium chloride dimer are
different (2.85 and 3.00 ppm respectively).101 The same splitting of NMez
protons were observed in this case for the methyl complex (_5_8_), indicating
the obvious diastereotopic nature of these methyl groups. The two peaks appeared
at 2.31 and 3.21 ppm respectively (see Figure 9). The chemical shifts of the
two methyl groups in NMe2 of the metal complexes (gig-Q), are much more
downfield than those of the corresponding free ligands and the chemical shift
difference of the two methyl groups (0.90 ppm) is large because the inversion

of the pyramidal N of these metal complexes is inhibited by a rigid 6-member

Tabkis

Metal-8, Metal-N, and Metal-Cl Stretching led. in Several Metal Complexes

Compound

dC12

Thioether-metal complexes
Unidentete amine-Metal complexes

( PllSC3H58Ph)?dC12

a This work.

V, cm"1

460 sh
320 b
300 b
465 sh
322 b
482 sh. 443 b
323 b
298 sh

460 sh

273, 316

349. 396

.280-400

370-500
278 sh, 262 sh

323 sh, 308 sh

Stretching lode

Pd-N
Pd-Cl. Pd-S,
Pd-Cl. Pd-S
Pd-N
Pd-Cl, Pd-S
Pd-N
Pd-Cl, Pd-S
Pd-Cl, Pd-S
Pd-N

Pd-Cl. Pd-S

Pd-Cl

Pd-S

Nl-S
hl-N
Pd-Cl

Pd-S

Reference

102

103

103

104

 

 

69

 

 

 

 

 

 

Figure '3. 250 MHz 1H NMR spectrun of _5_§; Pdffl2 complex.

r--.

 

70

chelate ring structure in the complex (see structure).

3. Infrared Spectra (IR)

The metal-N, metal—Cl, and metal-S stretching modes of several complexes
are given in Table 5. The most striking change occurs in the low frequency
region where metal-ligand vibrations are prevalent. Metal-sulfur bands are
often weak and occur in a region similar to metal-chloride bands. Consequently,
the absorptions around 297 to 323 cm‘1 region in complexes 22, Q, Q, and
§_3_, have been assigned to Pd-S and/or Pd-Cl stretches. Metal-nitrogen stretches
occur at a higher frequency region, so the peaks around 460 to 482 cm‘1 region
are assigned to Pd—N in the complexes. These assignments are, however, tentative
since in complex molecules of low symmetry, more than one fundamental mode;
often contributes to a given peak.105 It should be noted that the stretching A
frequencies assigned to complexes 5_9_, 60, 6_2_ and 63 are in close agreement
with those reported for the chelated thioether complex, (PhSC3HSSPh)PdC12,104

and most other values in the literaturemsv107

4. Structure of Dichloro[(_l_l_)-l-(_S_)-2-methylthioferrocenylethyldi methyl-
amine]pa]ladium(11), §_8_.

The structure and numbering scheme of dichloro[(_f_{_)-1-(_S_).2-methylthiofer-
rocenylethyldimethylaminelpalladiumfl1), §_8_, is shown in Figure 10, while
a stereoview is given in Figure 11. Hydrogen atoms have been omitted for
clarity. A total of 2937 reflections were collected, of which 2912 were unique
and not systematically absent. As a check on crystal and electronic stability,
three representative reflections were measured every 45 reflections. The
slope of the least-squares line through a plot of intensity versus time was -17

(16) counts/hour which corresponds to a total loss in intensity of 0.396. A linear

771‘

 

Figure 10: Structure and Numbering Scheme for the Comples
C5H5FeC5H3[CHMeNMe2][SMel/PdC12, fl

72

 

Figure 11:

Stereoview of the Complex C5li5FeC5H3ICHMeNMeZIISMel/PdClz, fl

73

decay correction was applied with correction factors on 1 ranging from 1.000
to 1.003 and with an average value of 1.002. The final coefficient, refined
in least-quares, was -0.344 x 10’8 (in absolute units).

The positional parameters are given in Table 6, while general temperature
factor expressions are given in Tables 7-9. The palladium atom is in a square
planar environment where the ferrocenylamine thioether ligand chelates to
the palladium atom through nitrogen and sulfur atoms.

The bond distances and bond angles for the complex are presented in Table
11 and Table 12 and are fairly typical. the iron-carbon distances range from
2.02(6) A to 2.050(6) A with an average value of 2.033(7) A that compares
favorably with that of ferrocene108 and 1,1'-bis(siobutylthio)ferrocene palladium-
dichloride.42 The carbon-carbon distances in the cyclopentadienyl ring vary -
from 1.378(12) A to 1.429(7) A, averaging at 1.407(1) A, a value typical of
ferrocene. The C-C-C bond angles within the two rings vary from 106.7(7)
to 109.2(7)°, with an average angle of 108.01° that is the typical angle for
a regular, planar pentagon.

The Pd-S bond length is 2.288(1) A which compares favorably with the
sum of the covalent radii (2.35 A)109 and suggests that there is little or no
1! -bonding in the Pd—S bond. The Pd—Cl bond, which is trans to the sulfur atom,
shows no apparent trans bond lengthening, indicating that the thioether ligand
has a negligible trans-influence.110 The Pd-Cl bond distances have an average
value of 2.307(5) A almost equal to the. sum of the Pauling covalent radii, 2.31
A.109 The Pd-N bond length is 2.159(4) A, and is comparable to the sum of
' the Pauling covalent radii.

Seyferth111 has reported a crystal structure of a heterobinuclear species
(Ph3P)PdFe(C5H4S)2 where thiolate groups chelate to palladium. The cyclopent-

adienylthiolato groups, (C5H4S), are tilted away from the parallel plane by

74

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75

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76

Table'f General Temperature ?ac:or Expressions - 3’s - for
chnlorofiR)-1-(S)-2-methylthioferrocenylechyldzaechylaslnelpalladzuatrr)

C9

C10
C11
C12
C13
C14
C15

1.96i1)
2.08(2)
3.75(6)
$.35<8)
2.92(5J
2.5(2)
4.1(2Y

.3.5(2)

3.0(2)
4.8(3)
2.5(2)
2.6(2)
2.7(2)
3.4(2)
2.3(2)
4.7(3)
3.8(3)
2.8(2)
7.1(4)
3.7(3)
6.3(4)

2.75(1)
3.30(3)
6.25(9)
5.42(8)
2.92(5)
2.6(2)
5.1(3)
3.2(2)
2.5(2)
3.4(3)
3.2(2)
4.8(3)
5.0(2)
2.8(2)
2.5(2)
4.7(3)
5.9(4)
7.4(4)
5.9(4)
8.7(4)
4.3(3)

B(3.3)

2.99<l)
2.91(3)
4.45(7)
7.5(1)
2.54(5)
2.1(2)
1.9(2)
4.5(3)
2.4(2)
5.1(3)
2.4(2)
3.1(2)
4.4(2)
4.6(3)
2.6(2)
6.9(3)
3.2(3)
6.6(4)
3.9(3)
4.3(3)

8(1.2)

‘0.17(2)
O.12(3)
-1e13(7,
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0.27C5)
0.2(2)
-O.1(2)
1.0(2)
'O.1(2)
'0.9(3)
'O.2(2)
“0.4(2)
1.0(2)
'0.2(2)
O.2<2)
‘0.2(4)
‘1.3(3)
1.1(3)
'O.9(4)
'1.2(3)
0.2(3)

3(1.3)

O.ZO(1)
-O.29(2)
-O.97(6)
'0.19(9)

O.23(4)

0.1(1)

0.3(2)
~O.7(2)
-O.4(2)
-O.9(3)

0.1(2)

0.5(2)

0.1(2)
-O.9(2)
-0.3(2)
“1.1(3)
—O.3(3)
'1.8(3)
‘3.3(2)
-0.0(2)
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B<2.3)

0.01(1)
-O.57(3)
-O.92(7)

2.03t8)

O.47(§)

0.4(1)
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0.3(2)

0.2(2)

1.1(3)
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-O.5(2)
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0.2(3)
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2.0(3)

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2.553(3)
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77

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Amvth0.0i .mvvw00.01 Adeoo.0 nvvmmO0.0 «FVVNH0.0 nthmO0.0 NHO
nmvNNOO.OI advaOO.OI AavaO.OI AVVVWO0.0 nmvmmO0.0 n0ded0.0 «H0
nmvdvoo.01 anvvoo.01 «NV«OO.OI nmvfinoo.o n?vaO0.0 nmvan0.0 Odo
amv0000.01 .vaHOO.OI «hthO0.0 “Nymmoooo Adevoo.O Anv0w00.0 m0
«OvVNOO.OI AQVMMOO.OI nmvnHO0.0 nflvmvoo.0 «VCOVO0.0 nthOd0.0 00
AmvmwOO.OI .hvmooo.o .Hv¢O0.0 anwVO0.0 n?vmmoo.0 awvmhoo.o ho
vadNOO.OI .mvmuoo.0 AHVNOO.OI «NVNNO0.0 Amv«QO0.0 amvmhoo.o W0
AnvNHO0.0n .wvmooo.o AQVHHOO.OI anmNO0.0 n?vmmoo.0 Anvmhoo.o n0
AhvaO0.0 anvmoo.0a «fivv00.01 nmvvnO0.0 n?vwm00.0 AmvNVH0.0 VD
AnvaO0.0 .hvaOO.OI AQVNOOO.OI ANvaO0.0 «fivaO0.0 awvmooo.0 m0
nmvoOO0.0 .vaNO0.0| Amvvv00.0 anvhvoooc «fivvnO0.0 nhvaH0.0 N0
nwvaOO.OI nhvo«O0.0 AdeOO.OI anONoooo nmvmmoooo a$vmddo.0 d0
Avvfinoo.0 .va000.0 .hthO0.0 anflwoooo nmvvv00.0 nflvth0.0 dz
advme0.0 ANVQOO0.0 ANVN.O0.0 anvmeO0.0 AmvaVO0.0 advaO0.0 «m
anva0.0 .mthOO.OI AGVVN«O.OI nanhOOsO nHvaO0.0 anhmH0.0 NAG
ANVVNOO.OI «vamoo.01 .vamOO.OIahvmwvoo.O «anO«0.0 anOAH0.0 «do
.thnHOO.O|nmvm0aOO.OI «HVWOO0.0 amvvomO0.0 Anvmnw00.0 nhvmomO0.0 «Oh
nvvv0000.0 .vahOO0.0 .hvthOO.OIAvadmOO.O andeO0.0 anvnhwoo.o va
Ameflvm Amedvm AN.avm «momvm «NeNvm «Hedvm Oloz.

...oas.oo..oo.oc.ao.scoos.o.«can.scououuemo.zu.sauo=-~-.m.-.-.mo.ouo.cu.c
no.“ i o‘euom I ecofinuouaxm noun-...... eunuch-«mew... Uncamom .m Dana...

78

.eucoumcou ovauuoa douchnduou one 0 Use .n .e Duos)
n..m.NcsunHXN o .m.dv=Uo~£N o «N.nv:noxnw o

.m.vaNUNH 4

.«.«o=«n«x .

....0=«o«z.«e«-.axe
no. nouosouon «canon» DwaOhuoewce and mo show och

.m.n«o.o .eomoo.o- .vo«oo.o .v..mo.o .vvvmo.o .m.m«o.o n.0

....mo.ou .moooo.o- .v.o.o.o- .m.mvo.o .ooo...o .v.«vo.o v.0

..omoo.o .m0.eo.o- .n0«.o.o- .monno.o .novno.o .moomo.o «.0

.vonmo.o- .m.m«o.o- .vov.o.o .vcvmo.o .movmo.o .monmo.o «.0

.....o.o- .vovoo.o- .v00.o.ou .vommo.o .momno.o .moovo.o ..0

.m.o«o.o- .vom.o.o- .nomoo.o- .m0.mo.o .nommo.o .v.ooo.o o.0

.«.voo.o- .«.voo.o- .«.«oo.o .«ovmo.o .«..mo.o .«oomo.o m0

.m0«.o.o- .m0«.o.o- .mvmoo.o .momno.o .m.mmo.o .momvo.o 00

.mcomo.o- .mo.oo.o .mom.o.o .mommo.o .m.mmo.o .movmo.o «0

.moo.o.o- .«omoo.o .mcmoo.o- .m.mmo.o .m..mo.o .«.mmo.o 00

.«.moo.o- .«.«oo.o .«omoo.o- .«..mo.o .m.ovo.o .«..mo.o n0

.m...o.o .v...o.o- .mo..o.o- .v.nmo.o .momvo.o .v..mo.o v0

.«.moo.o .«.moo.o- .«..oo.o- .«..mo.o .«.«mo.o .«oomo.o m0

.movoo.o .m.moo.o- .mom.o.o .mommo.o .m..vo.o .mcmvo.o «0

.mcmoo.o- .movoo.o .mo.oo.o- .«vvmo.o .vcmmo.o .m..no.o .0

.«.woo.o .«..oo.o .«.«oo.o .«.««o.o .«ommo.o .«.«mouo .z

.oooooo.o .mom«oo.o .wcvmoo.o .0o««mo.o .«oonmo.o .momomo.o .m
...o«o.o ...«oo.o- .ocmmmo.o- ..onmo.o ..ommo.o ...omo.o «.0

.m.«..o.o- .«.m«.o.o- .m.mv.o.o- .movmno.o ..omno.o .«ovnvo.o ..0
.m.««oo.o- .m.«moo.o- .mcm.oo.o .moowmo.o .v.m.vo.o .m.mm«o.o .ou
.«.«ooo.o .«ommoo.o .«o««oo.o- .«.mnmo.o ..omvmo.o ..oo.«o.o .oa
.m.«o= .m...: .«..o: .m.moa .«.«.= .....a one:

....s:.oo..oo.wc.so.scoos.o.«coo.scououuomo.zu.szuon-«u.m.-.-.mo.ouo.zu.o
how u 0.: I occunmouaxw uouuom muaueuQQEOP achocou .moénoh

79

GON.O NQN.O hhd.o WHO
vnm.O QHN.O HQH.O VHO
ovm.o QwN.O OwH.O MAO
vmm.o mmm.0 «0H.O NdU
N@N.O mmN.O me.O «do
QQN.O OWN.O hQH.O 0H0
wmd.0 mod.o an.O m0
HmN.O vmd.o Ohd.o Q0
Nom.0 HON.O th.O ho
th.O mwd.o OhH.O $0
mON.O Vba.o th.O W0
bQN.O QNN.O wmfl.0 v0
VON.O OmH.O va.O m0
mVN.O mNN.O mmd.0 NU
mnN.O hNN.O MWH.O AU
mmH.O mhd.o mmH.O Hz
mON.O mmu.o 00H.O «m
hvm.o QQN.O mmH.O NHO
va.O mmN.o wha.o AAU
QHN.O Oma.0 QWH.O How
wm..0 mma.o wma.0 «Um
.xox .UossuCH .cqx louc

....s:.oo..oo.oc.so.scoos.o.«coo.scououuowo.au.scoox-«n.mo-.-.m..ouo.no.o
how .esouuomcc Gav co.ueun.> Hoeuock MO confidaaaec ouoavmuceozluoom .opeannh

80

«dehmm.a vac MAO

«aayhmv.a mdo NHU
«Ndvmhm.d NdO «do
«Oavmmm.a VHO 0H0
«Havwmm.d «do OHU
nQvOnv.H mo 00
nmvoav.d 00 N0
nmvhov.d ho m0
.vawv.d m0 W0
nhvav.d 00 00
.hvmmv.d 00 m0
Amvmdw.d #0 m0
nhvan.d m0 «2
Amvwow.d NO d2
nhvhwv.d H0 H2
amvmmh.d. 0&0 Hm
AnymVB.H $0 am
nhvva.N VdU «Oh
nhvhmO.N GAO «Oh
«FVVNO.N «do Hon
AQVmNO.N HMO Ham
ABVNVO.N 0H0 «Oh
nmvNNO.N 00 «ch
anHNO.N 00 «Oh
Amvmm0.N ho Ham
nmvomO.N 00 «Oh
amvwv0.N flu dom
avvmn«.N Hz HUQ
«AVQQN.N H” «Um
ANVHQN.N NHO «Um
«vamm.N HAO «Um

oucouo.o «sou< .souc

....s:.co..oo.oc.ao.«nuos.o.scuo.>cououuomo.nu.scuoz :« .no :. .m..ouo.no.c
«om .esouunmcc :4. eoucoue.o Ucom .PpoHnoh

81

.ou.m.o ucou.m.cm.n anon. on» c.
ocoHueH>0U UuoUcoue UouoEHuoo who oooozucouoa CH ohoniaz

nthQ.O 00H: DHO
.hvmm.o nnH: “HO
nmv00.0 onH: nHO
.vaQ.O VH2 VHO
Amva.H NH: mHO
.mvmm.0 NH: NHO
.mvom.0 HH: HHO
Ahvoo.0 OH: OHO
nwva.O Q: 00
Anvwm.0 hm BO
nwvhm.o O: OO
.mva.O UV: VO
.hvhh.0 AV: VO
nvaO.H 0V: VO
nmvmm.0 m: MO
.hvhm.0 UN: NO
.vaO.H an NO
.mvmm.o 0N: NO
.wvmh.0 OH: HO
.wvmm.0 DH: HO
AmVOH.H 0H: HO

oucooo.o «none .nou<

...ona.oo..oo.oc.so.«coos.o.«coo.scooouuomo.nu.snuozu«u.m.-.-.m0.ouo.zu.v
how «UNDEHuCOOv noucounHo Ucom

82

- Tehle12- Bond Angles (1n Degrees) for
d1chlorol(R)-1-(3)-2-Hethy1thioferrocenylethyldteethylaslne)pelledlue<II)

Atoel Ate-2 Atosa Angle
............... -.---
011 P01 C12 87.79(8)
Cll Pdl 51 178.34(6)
C11 Pd1 N1 90.9(1)
C12 Pd1 51 90.55(7)
C12 Pd1 N1 177.9(1)
31 Pdl N1 90.8(1)
CS Fel - 06 40.8(2)
C5 Fel C7 68.6(2)
C5 Fel C8 68.9(2)
C5 Fe1 C9 41.0(2)
C5 Fel C10 110.0(3)
CS Fe1 C11 125.2(3)
C5 Fel C12 159.8(3)
C5 Fe1 C13 158.3(3)
C5 Fe1 C14 124.3(3)
C6 Fe1 C7 40.3(3) - L
C6 Fe1 C8 68.4(3)
C6 Fel C9 68.5(2)
C6 Fel 010 A 122.6(3)
C6 Fe1 C11 107.2(3)
C6 Fe1 C12 122.2(3)
C6 Fel C13 159.2(3)
C6 Fel 014 158.9(3)
C7 Fe1 C8 40.9(3)
C7 Fe1 C9 68.6(2)
C7 Fe1 C10 155.7(3)
C7 Fel C11 119.4(3)
C7 Fe1 C12 105.1(3)
C7 Fel C13 122.9(3)
C7 Fe1 C14 160.6(3)
CB Fe1 C9 40.8(2)
C8 Fe1 C10 163.1(3)
C8 F31 C11 154.4(3)
C8 Fol C12 119.6(3)
C8 Fol C13 106.8(3)
CB Fe1 C14 125.6(3)
C9 Fe1 C10 127.3(3)
C9 Fel C11 163.1(3)
C9 F31 C12 156.4(3)
C9 Fel C13 22.0(3)
C9 Fol C14 110.5(3)
C10 Fel C11 40.1(3)
C10 F61 C12 67.4(3)
C10 F91 C13 67.6(3)
C1 F91 C14 40.0(3)

C11 Fel C12 39.3(3)

83

Bond Anglee (Contlnued) for
dlchlorot(R)-1-(S)-2-Nethylthloierrocenylethy1dlnethyleelnelpelledlun(11)

Ate-1 Atoe2 Ate-3 Angle
C11 Fel C13 67.9(3)
C11 Fel C14 67.3(3)
C12 Fe1 C13 41.1(3)
C12 Fel C14 67.6(3)
013 Fel C14 39.8(3)
961 51 C9 97.3(2)
Pdl 51 C15 114.5(3)
C9 51 C15 100.8(3)
Pdl N1 C1 108.5(4)
Pdl N1 C2 104.5(3)
Pdl N1 C3 116.1(3)
C1 N1 CZ 108.9(4)
C1 N1 C3 109.2(4)
C2 N1 C3 109.4(4)
N1 C3 C4 115.1(5)
N1 C3 C5 108.3(4)
C4 C3 C5 113.0(5) _ ;
Fel C5 C3 130.6(4)
Fel C5 C6 69.7(3)
Fel C5 C9 68.6(3)
C3 C5 C6 132.1(5)
C3 C5 C9 120.8(5)
C6 C5 C9 106.8(5)
Fel C6 C5 69.5(3)
Fel C6 C7 69.4(3)
65 06 C7 108.5(5)
Fel C7 C6 70.3(3)
Fe1 C7 C8 68.9(4)
C6 C7 C8 108.2(5)
Fe1 C8 C7 70.2(4)
F01 C8 C9 69.6(3)
C7. C8 C9 108.0(5)
F61 C9 51 130.0(3)
Fol C9 C5 70.4(3)
Fel C9 C8 69.5(3)
51 C9 05 117.5(4)
51 C9 08 133.7(4)
C5 C9 C8 108.6(5)
Fel C10 C11 69.2(4)
Fe1 C10 014 69.7(4)
C11 C10 C14 107.3(7)
Fe1 611 C10 70.6(4)
F01 C11 C12 70.1(5)
C10 C11 - C12 108.9(7)
Fel C12 C11 70.1(4)

Fol C12 C13 59.9(4)

84

Bond Anglee (Contlnued) for
dlchlere((R)-1-(5)-2-Nechylthloferrocenylethyld1nethyleelne)pelledlue(11)

Ate-1 Ate-2 Ate-3 Angle

C11 C12 C13 107.9(7)
F01 C13 C12 68.9(4)
Fe1 C13 C14 70.0(4)
C12 C13 C14 106.7(7)
F01 C14 C10 70.3(4)
Fe1 C14 C13 70.2(4)
C10 C14 C13 109.2(7)
H1 C1 H1. 111.(3)
H1 C1 H1b 116.(4)
N1 C1 H1c ' 114.(5)
H18 C1 H1b 99.(5)
H1e C1 H1: 113.(6)
H1b C1 H16 102.(6)
H1 C2 H2. 108.(5)
N1 C2 H2b 107.(3) .
H1 C2 H2: 111.(5) '
H28 C2 H2b 102.(6)
H28 C2 H2: 107.(6)
H2b C2 H2: 121.($)
H1 C3 H3 103.(4)
C4 C3 H3 107.(4)
C3 C3 H3 110.(4)
C3 C4 H4. 109.(4)
C3 C4 H4b 109.(3)
C3 C4 H4: 112.(3)
H4e C4 H4b 109.(6)
H4e C4 H4c 103.($)
H4b C4 H4: 114.(6)
Fel C6 H6 118.(4)
C5 C6 H6 121.(4)
C7 C6 H6 129.(4)
Fel C7 H7 124.(3)
C6 C7 H7 132.(3)
C8 C7 H7 120.(3)
Fe1 C8 H8 134.(4)
C7 C8 H8 128.(4)
C9 C8 H8 123.(4)
Fel C10 H10 123.(4)
C11 C10 H10 117.(4)
C14 C10 H10 135.(4)
Fol C11 H11 128.(6)
C10 C11 H11 11$.(6)
C12 C11 H11 136.(6)
Fol C12 H12 126.(4)

C11 C12 H12 126.(4)

85

.ouqmau unavamacmflu one." as» ea
u:o«uo«>ov vuovcoue uouoeaueo one eoeonucouon ad Ihoneaz

.oC.nH« on“: mac and:
168.6m on": mac on”:
“08.naa an“: mac and:
Anv.v«« on”: ado «m
nvv.mo~ an”: mac «m
Anv.naa on”: man an
.nv.~m« v": «do mac
Anv.mufl v“: vac ode
Amv.owd v5: «50 «on
.vv.um« mu: mac vuo
Avv.«~a ma: ago «do
nvv.maa max «do «om
Avv.mma max «do mflo
camcc msouc «souc «nouc

.HHV-aauoadoa.ocquoauzuosaudxcuoaxenoouuomoazuaxcuo=-~-Amv-a-Amvuouoqnouv
Mom “Canaaucoov eo~mc< neon .

86

Teble13- Torelonel Anglee (ln Degreee) {or
dlchloro((R)-l-(5)-2-Hethylth1o£errocenylethyldleethylenlne)pelledlue<II)

Atoe 1 Atoe 2 Atom 3 Atoe 4 Angle

C11 P61 51‘ C9 131.3
C11 961 51 C15 25.9
C12 901 51 C9 127.3
C12 P41 51 C15 21.8
H1 Pd1 31 C9 '54.3
H1 Pd1 51 C15 -159.8
-C11 Pd1 H1 C1 -52.1
C11 Pd1 H1 C2 64.0
C11 Pd1 H1 C3 -175.4
'C12 Pdl H1 C1 -102.7
C12 Pd1 H1 C2 13.4
C12 Pd1 H1 C3 134.0
51 Pd1 H1 C1 128.1
31 P61 H1 C2 -115.9
31 Pd1 H1 C3 4.8
C6 F01 C5 C3 -128.7
C6 F01 C5 C9 118.5
C7 F01 C5 C3 -165.6
C7 F01 C5 C6 -36.9
C7 F01 C5 C9 81.6
C8 F01 C5 C3 150.4
C8 F01 C5 C6 -80.9
C8 F01 C5 C9 37.6
C9 F01 C5 C3 112.9
C9 F01 C5 C6 -118.5
C10 F01 C5 C3 ‘11.5
C10 F01 C5 C6 117.2
C10 F01 C5 C9 -124.4
C11 F01 C5 C3 -53.9
C11 F01 C5 C6 74.8
C11 F01 C5 C9 -166.8
C12 F01 C5 C3 -90.3
C12 F01 C5 C6 38.3
C12 F01 C5 C9 156.8
C13 F01 C5 C3 68.0
C13 Fe1 C5 C6 -163.3
C13 F01 C5 C9 -44.9
C14 Fel C5 C3 30.9
C14 F91 C5 C6 159.6
C14 Fe1 C5 C9 -81.9
C5 Fe1 C6 C7 -120.2
C7 Fe1 C6 C5 120.2
C8 Fel C6 C5 82.4
CS Fel C6 C7 -37 8
C9 Fel C6 C5 38.3
C9 Fel C6 C7 -61.9

C10 Fel C6 C5 '83.1

87

Toretonal Anglee (Contlnued) for
dlchloro((R)- -1-(5)-2-Nethylthloterrocenylethyldlnethylaelne)pelled1un(11)

Atoe 1 Atoe 2 Atoe 3 Atoe 4 Angle

C10 F01 C6 C7 156.7
C11 F01 C6 C5 -124.4
C11 F01 C6 C7 115.4
C12 F01 C6 C5 -165.3
C12 F01 C6 C7 74.5
C13 F01 C6 C5 162.6
'C13 F01 C6 C7 42.5
C14 F01 C6 C5 -53.0
C14 F01 CG C7 -173.2
'C5 F01 C7 C6 37.4
C5 F01 C7 ' C8 ~82.1
C6 Fe1 C7 C8 -119.5
C8 F01 C7 C6 119.5
C9 F01 C7 C6 81.6
C9 F01 C7 C8 -37.9
C10 F01 C7 C6 -54.1
C10 F01 C7 C8 -173.6
C11 F01 C7 C6 -82.0
C11 F01 C7 C8 158.5
C12 F01 C7 C6 -122.4
C12 F01 C7 C8 118.1
C13 F01 C7 C6 -163.4
C13 F01 C7 C8 77.1
C14 F01 C7 C6 172.6
C14 F01 C7 C8 53.1
C5 F01 C8 C7 81.2
C5 F01 C8 C9 -37.7
C6 F01 C8 C7 37.2
C6 F01 C8 C9 ~81.7
C7 F01 C8 C9 -118.9
C9 F01 C8 C7 118.9
C10 Fe1 C8 C7 170.9
C10 F01 C8 C9 52.0
C11 F01 C8 C7 -47.6
C11 Fel C8 C9 -166.5
C12 F01 C8 C7 -78.5
C12 Fe1 C8 C9 162.6
C13 Fol C8 C7 -121.3
C13 F91 C8 C9 119.8
C14 Fol C8 C7 ~160.9
C14 F91 C8 C9 80.2
C5 F31 C9 31 -109.9
C5 Fe1 C9 C8 119.5
C6 Fe1 C9 51 -148.1
C6 F31 C9 C5 -38.2
06 Fel C9 C8 81.4

C7 Fe1 C9 51 168.5

Toreional Anglee (Contlnued) for

Atoe 2 Ato-
Fel C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C9
Fe1 C10
Fe1 C10
Fe1 C10
Fe1 C10
Fe1 C10
Fe1 C10
Fe1 C10
Fe1 C10
Fe1 C10
Fe1 C10
Fe1 C10
Fe1 C10
Fe1 C10
Fe1 C10
Fe1 C10
F01 C10
Fe1 C11
Fe1 011
Fe1 C11
F01 C11
Fe1 C11
F01 C11
F01 C11
Fel C11
Fe1 C11
F01 C11.
F91 C11

88

3 Atoe 4

37.1

89

Torelono1 Anglee (Contlnued) for
dlchloro((R)-1- (S)-2-Nethy1th1o£errooeny1ethyldlnethyloelneJpelledlue(11)

Atoe 1 Aton 2 A80: 3 Atoe 4 Angle

012 r.1 C11 010 -119.5
C13 r.1 011 010 -61.0
C13 r.1 C11 C12 38.5
c1. r.1 C11 C10 -37.7
01. 3.1 011 012 81.8
cs 9.1 C12 011 49.3
“cs r.1 C12 013 166.0
‘C6 Fe1 C12 011 77.9
C6 r.1 012 C13 -163.3
- 07 3.1 012 011 118.1
07 r.1 012 013 -123.2
C8 Fe1 C12 011 159.7
C8 r.1 C12 013 -81.5
09 r.1 C12 011 -171.0
09 r.1 012 013 -52.3
010 r.1 012 011 -37.4
c10 r.1 C12 013 81.3
011 Fe1 012 013 118.7
013 r.1 C12 011 -116.7
014 r.1 C12 011 -60.9
014 r.1 012 013 37.6
c: r.1 013 C12 ~166.6
cs r.1 013 C14 -so.9
C6 r.1 C13 C12 43.0
C6 r.1 013 014 160.9
07 r.1 C13 C12 74.3
07 r.1 013 01. -167.8
ca Fe1 013 012 116.1
ca r.1 013 014 -126.0
c9 F.1 C13 C12 158.1
09 F01 C13 C14 -84.0
C10 r61 c13 C12 -6o.6
C10 F01 C13 C14 37.0
011 3.1 C13 C12 -37.3
C11 3.1 C13 C14 60.6
c12 Fe1 013 C14 117.9
614 r.1 C13 c12 -117.9
cs Fol C14 010 -60.3
05 r.1 C14 C13 159.6
C6 r.1 014 C10 -41.1
C6 Fe1 C14 013 -161.1
c7 Fe1 014 010 152.3
7 3.1 C14 C13 32.2
C8 F81 C14 C10 -167.7
cs 3.1 C14 c13 72.3
C9 Fe1 C14 610 -124.2
C9 F01 C14 C13 115.8

C10 F81 C14 C13 '120.0

90

Torelonol Anglee (Contlnued) {or
d1ohloro((R)-1-(5)-2-Nethylthloferrooenylethyldtnethylonlne)pallodlue(II)

Aton 1 Atoe 2 Atoe 3 Atoe 4 Angle

611 9.1 C14 610 '37.8
611 9.1 614 C13 -82.2
612 9.1 614 C10 61.1
612 9.1 614 C13 -39.0
C13 9.1 C14 C10 120.0
Pdl 51 C9 9.1 149.1
.Pdl s1 69 65 62.3
Pd1 s1 69 66 -111.1
C15 51 C9 9.1 -94.1
-615 51 C9 C5 179.1
615 51 69 66 5.7
Pdl N1 63 C4 -176.9
Pdl N1 C3 C5 55.6
61 N1 63 C4 60.2
C1 N1 63 65 -67.4
02 N1 63 C4 -58.9
62 N1 63 C5 173.5
N1 C3 C5 9.1 -157.9
N1 C3 65 C6 102.9
N1 63 C5 69 -70.7
C4 63 C5 -;.1 73.3
C4 63 C5 C6 -25.9
C4 C3 C5 C9 160.5
9.1 C5 C6 67 58.6
63 65 66 9.1 127.0
63 C5 C6 C7 -174.4
C9 C5 C6 9.1 -56.6
C9 65 C6 C7 -0.2
9.1 ‘ 65 69 51 125.7
9.1 65 c9 66 -59.3
C3 65 C9 9.1 -125.5
63 65 69 51 0.2
C3 65 c9 66 175.2
66 65 C9 9.1 59.5
' 66 65 69 51 -174.8
66 C5 C9 66 0.2
9.1 66 67 66 56.7
C5 C6 67 9.1 -56.6
C5 66 67 66 0.1
9.1 C7 C8 69 59.6
66 C7 66 9.1 -59.6
C6 C7 66 69 0.0
9.1 66 C9 51 -126.3
9.1 66 69 C5 59.6
c7 66 69 9.1 -60.0
67 66 69 51 173.6

C7 C8 C9 C5 -0. 1

91

Torelonol'Anglee (Continued) to:
dlohloto((R)-l-(5)~2-Nethylthloferrooenylethyld1eethlonlne)pollodlun<II)

. ----------------q---- ------- ............

Atoe 1 Atoe 2 Atoe 3 Atoe 4 Ang1e

------ -q---- ------ ---- .......

9.1 610 C11 612 -59.9
614 C10 611 9.1 ,59.5
C14 610 611 612 -0.4
9.1 C10 C14 C13 59.6
C11 610 614 9.1 -59.2
C11 C10 C14 613 0.4
'9.1 C11 612 613 -60.0
'610 611 612 9.1 60.2
610 611 612 C13 0.3
. 9.1 C12 613 614 -60.1
611 612 C13 9.1 60.0
611 612 613 614 0.0
9.1 613 614 610 -59.6
612 C13 014 9.1 59.4
612 613 614 610 -0.2
65 9.1 66 N6 115.6
67 9.1 66 N6 -124.3
66 9.1 66 N6 -162.1 _
69 9.1 66 N6 153.9 . -
610 9.1 C6 N6 32.4
C11 9.1 66 N6 -6.6
C12 9.1 66 N6 -49.6
613 9.1 66 N6 -81.8
C14 9.1 C6 N6 62.6
65 9.1 67 N7 164.9
C6 9.1 67 N7 127.5
C8 9.1 C7 N7 -113.0
69 9.1 C7 N7 -150.9
610 9.1 67 N7 73.4
611 9.1 67 N7 45.6
612 9.1 67 N7 5.1
613 9.1 C7 N7 -35.9
014 9.1 67 N7 -59.9
65 9.1 66 N6 -154.9'
C6 9.1 66 N6 161.1
C7 9.1 66 N6 123.9
69 9.1 66 N6 -117.2
610 9.1 66 N6 -65.2
C11 9.1 66 N6 76.3
612 9.1 66 N6 45.4
C13 9.1 66 N6 2.6
C14 9.1 66 N6 —37.0
65 9.1 610 N10 -11.4
66 961 C10 N10 32.3
67 961 610 N10 70.6
66 9.1 C10 N10 -94.7
c9 961 610 N10 -54.3

92

- Toretonol Anglee (Continued) to:
dlohloro((R)-1-(5)~2-Netnylthlo£errooenylethyld1nethyloelne1pelledlue<II)

Aton 1 Aton 2 Atoe 3 Atoe 4 Angle

C11 9.1 610 N10 109.9
C12 9.1 C10 N10 147.1
613 9.1 610 N10 -166.2
C14 9.1 610 N10 -131.3
65 9.1 C11 N11 -27.9
66 9.1 611 N11 13.4
.67 9.1 C11 N11 55.5
66 9.1 C11 N11 69.2
C9 9.1 C11 - N11 -59.1
- 610 9.1 C11 N11 -107.1
612 9.1 611 N11 133.4
613 9.1 C11 N11 171.9
014 9.1 611 N11 -144.6
C5 9.1 612 N12 -70.9
66 9.1 C12 N12 -42.3
67 9.1 612 N12 -2.1
66 9.1 C12 N12 39.5
69 9.1 C12 N12 66.6
610 9.1 C12 N12 -157.7
611 9.1 C12 N12 -120.2
C13 9.1 612 N12 121.1
C14 9.1 612 N12 156.6
65 9.1 C13 N13 76.4
C6 9.1 613 N13 -71.6
67 9.1 613 N13 -40.5
611 9.1 613 N13 -152.1
C12 9.1 613 N13 -114.6
C14 9.1 613 N13 127.3
66 9.1 613 N13 1.3
C9 9.1 613 N13 43.3
610 9.1 ‘ 613 N13 164.4
65 9.1 614 N14 42.6
66 9.1 614 N14 62.1
67 9.1 614 N14 -64.6
66 9.1 614 N14 -44.5
C9 9.1 614 N14 -1.1
610 9.1 614 N14 123.2
611 9.1 614 N14 161.0
C12 9.1 614 N14 -155.6
C13 9.1 614 N14 -116.6
961 51 615 N15. -57.6
961 31 615 Hlsb 177.0
961 51 615 H15C 52.3
69 51 615 H150 -160.6
C9 51 615 Hle 73.7
C9 51 615 N156 -50.9

Pdl N1 C1 H15 -69.0

93

- Tore1one1 Anglee (Contlnued) for
dlohloto((R)-1-(5)-2-Nethylthloferrooenylethy1dlnethyloelne)pollodlue(11)

Atom 1 Aton 2 Atoe 3 Atoe 4 Angle

961 N1 C1 N18 179.0
961 N1 61 N16 60.6
62 N1 C1 N1. 177.6
62 N1 61 N18 65.8
62 N1 C1 N16 -52.6
63 N1 61 N1. 56.4
63 N1 61 N18 -53.6
63 N1 Cl N16 ~172 o
961 N1 62 N2. 67 2
961 N1 62 N28 -42.1
961 N1 62 N26 -175 9
01 N1 62 N2. -177 0
61 N1 62 N28 73.7
61 N1 62 H2c -6o 1
63 N1 62 N2. -57.8
63 N1 62 N28 -167 1
63 N1 62 N20 59 1
961 N1 63 N3 -60.7
C1 N1 63 N3 176.3
62 N1 63 N3 57.3
N1 63 64 N4. 178.2
N1 63 C4 N48 56.6
N1 63 C4 N46 -66.7
65 63 64 N4. -56.7
C5 C3 C4 N48 -176.2
65 63 64 N46 56.4
N3 63 C4 N4. 64.6
N3 63 64 N48 -54.9
N3 63 64 N46 177.6
N3 63 CS 9.1 746.5
N3 63 65 66 -145.7
N3 63 65 69 40.7
9.1 65 66 N6 -11o.9
63 65 66 N6 16.1
C9 65 66 N6 ~169.6
9.1 C6 C7 N7 -119.1
65 , 66 67 N7 -177.7
N6 C6 C7 9.1 109.6
N6 66 67 66 166.5
N6 66 67 N7 -9.3
9.1 C7 66 N6 -131.5
66 c7 66 N6 ‘ 166.9
N7 67 66 9.1 116.5
N7 67 66 ' 69 176.1
N7 C7 66 N6 —13.0
N6 66 69 9.1 130.5

H8 C8 C9 51 4.2

94

0.“ Va: VHO Mao Max

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0....- .6: .v.0 0.0 . 0.:
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95

Tah1e14. Leaet-Squaree Planee for
dlchlorot(R)~1-(S)-2-Nethylthloferrocenylethy1dlnethy1aelnelpalladlu-(II)

The equatlon of the plane le of the fore:
AIx . BIy 0 CI: - D I 0

where A. 8. C 8 D are oonetante and

x. y 8 z are orthogonallzed ooordlnatee.

Plane No. l A I -0.4255. 8 I -0.5241. C I -0.7378, D I -12.9444
Chl Squared . 0.
Atoe x y z Dlotanoe End
5 ------------ Atoee 1n Plane -------------
C5 5.2802 13.0970 5.1980 -0.001 0.005
C6 6.5620 12.8976 4.5977 0.001 0.006
C7 7.1189 11.7152 5.1182 0.000 0.006
C8 6.1973 11.1620 6.0426 0.000 0.006
C9 5.0692 12.0072 6.0912 0.001 0.005
--------------- Other Atone--------------
C3 4.2053 14.1071 4.9545 0.107 0.005
31 3.5110 11.9000 6.8786 0.139 0.001
Fe1 6.7332 13.0177 6.6369 -1.639 0.001
H6 6.9837 13.5890 4.0663 -0.l49 0.060
N7 7.9680 11.2909 4.9684 -0.029 0.055
N8 6.2215 10.3403 6.4261 0.137 0.061
Plane No. 2 A I -0.4711. 8 I -0.4929. C I -0.7315. D I -16.0916
Chl Squared I 0.
Atom x y z Dletanoe End
------------- Atoea 1n Plane-------------
010 6.8304 14.7983 7.6312 -0.002 0.007
C11 8.0572 14.4931 7.0408 0.002 0.008
C12 8.5146 13.2994 7.5545 -0.001 0.008
C13 7.5498 12.8274 8.4934 -0.001 0.008
C14 6.5269 13.7643 8.5177 0.002 0.007
--------------- Other Atone--------------
F01 6.7332 13.0177 6.6369 1.648 0.001
H10 6.4149 15.5251 7.3522 0.039 0.065
H11 8.3760 15.1209 6.4773 -0.045 0.093
N12 9.3308 12.8743 7.3235 -0.007 0.058
H13 7.6284 11.8917 8.9107 0.118 0.073
814 5.8441 13.6453 8.9203 0.088 0.064

96

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97

Dihedral Anglee Between Planee:

Plane No. Plane No. Dihedral Angle
1 2 3.2
1 3 73.5
2 3 76.6

Table16 Dihedral Angle and Bridgehead Angle of Selected
[3]ferrocenophanes.

 

 

Dihedrala Bridgehead

 

Compound X I4 Angle Angle
0
° ' 3 Se 112.2° 100.5
Fe(CSHuS)2Qe o
H °) S S S llO.9° 103.9
Fe(cs “U 2 no 8U 0°
75. .
Fe(CSHuS-iBu)2PdC12 s Pd 93 so
‘ H6.6° .
Fe(CSHuAsMe2)2Ni(CO)I2 As hi

 

° lanes calcula-
a 1 an 1e obtalned from least-squares p 7
EiggdraDihegral angle refers to angle between FeX2 plane

and MX2 plane. “
6 1‘.

98

19.6. Seyferth proposed the presence of a weak dative Fe Pd bond on the
basis of a Fe-Pd distance of 2.878(1) A. The structure of the methyl palladium
complex, _5_Ԥ, makes it impossible for any interaction between Pd and Fe to
occur.

The two cyclopentadienyl rings are eclipsed and are slightly tilted with
respect to each other, the dihedral angle being, 3.2°. The planes containing
the cyclopentadienyl rings are almost orthogonal to the plane containing the
palladium, sulfur, nitrogen and chlorine atoms. Table 14 shows a list of atomic

parameters refined in least squares.

C. (§.§)-C5H5FeC5H3[CH(CH3)N(CH3)2HSCSHR2] (R = Me,Et)

The dithiocarbamate ligand has played a major role in the chemistry of
transition-metal sulfide complexes.112’1131114 Dithiocarbamates and thiuram
disulfides have been used as fungicides, pesticides, vulcanization accelerators,
antioxidants, floatation agents and high-pressure lubricants, and as drugs in
medicine.112 In particular, complexes of heavy metals with thiuram disulfides
are effective fungicides and seed disinfectants. The rich and diverse chemistry
of dithio acid and dithiolate complexes has been extensively covered in many

reviews.1 1 3

1. Preparation
Tatraalkylthiuram disulfides undergo nucleophilic attack at the disulfide

linkage by cyanide ions, amines and Grignard reagents.115 Cava116 has reported
that aryllithium derivatives react with tetraisopropylthiuram disulfide to give
dithiocarbamate esters that were precursors to aromatic thiols. Recently
McCulloch41 reported that dilithioferrocene and lithioferrocene reacted with

a series of tetraalkylthiuram disulfides giving rise to bis(dialkyldithiocarbamate)-

99

ferrocene derivatives and monosubstituted dialkyldithiocarbamateferrocene
derivatives respectively. Reaction of l-dimethylaminomethyl-Z-lithioferrocene
with tetraalkylthiuram disulfide also gave rise to l-dimethylaminomethyl-Z-
(dialkyldithiocarbamate)ferrocene derivatives.54

Reaction of (l_l_,_Ii)—1—dimethylaminoethyl-Z-Iithioferrocene, [(§)-(§_)-2_Z_].
with tetramethylthiuram disulfide and tetraethylthiuram disulfide gave rise
to a high yield of (_13_,_S_)-1-(dimethylaminoethyl)—2—(dimethyldithiocar
bamate)—ferrocene, fl, and (R,§)-1-(dimethylaminoethyl)-2-(diethyldithiocar-
bamate)ferrocene, 6_7_, respectively (Scheme 15). These new compounds contain
a chiral center and plane of symmetry that is absent in bis(dialkyldithiocarbamate)-
ferrocene derivates and dialkyldithiocarbamateferrocene derivatives.41 They
also contain a chiral center that is absent in 1-dimethylaminomethyl-Z-dialkyl- -
(dithiocarbamate ferrocene.54 In contrast to the results obtained by Cava,
only the desired product and no thioamide derivative was obtained. The thioamide

species arise from competing nucleophilic attack at the thione carbon rather

than at the sulfur—sulfur bond in the tetraalkylthiuram disulfide.

2. 1N NMR

The 250 MHz 1N NMR data for (fi,_S__)-1-(dimethylaminoethyl)-2—(dialkyl-
dithiocarbamate)ferrocene derivatives, :33 and £1, are given in Table 17. The
1H NMR spectra of these ligands are similar to the spectra obtained for the
chiral ferrocenyl-thioether compounds in the previous section, (Table 2). A
comparison of the chemical shifts of the substituted ring protons in Table
17 and Table 2 revealed that the SCSNR2 group substituted at ring exhibit
more downfield peak than SR substituted ring. This is to be expected since
the greater electron withdrawing effect of the SCSNR2 group causes a greater

deshielding of the ring protons, resulting in a more downfield peak.91192 At

100

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u-"Nmz R,NC5$CNR.
A

 

Fe I Fe IC'NRz
© © 5
R = Me, 66
@Hyfl R = Rt 67

Scheme 15

102

room temperature, single signal was observed for the NR2 protons of the carba-
mate group due to incomplete restricted rotation around the C-N bond. At
lower temperatures however, two separate signals were observed for the N,N--

dialkyl signals a phenomenon that will be discussed in detail later.

3. 13c NMR

The 13C NMR data for the chiral carbamate derivatives, fig and g are
given in Table 18. During acquisition of the 13C NMR data, the parameters
PW = 4 us and Rd = 4s were used since the thiocarbonyl carbon has a long relaxation
time, T1.42 The low field signal around 198.9 ppm is attributed to the thiocarbonyl
carbon. The other assignments shown in table 18 are tentative but results
from other work do support these
assignments“,54 The assignments of C3 < C4 < C5 are based on previous

conclusions about deshielding.41

4. Dynamic NMR Studies
There are two possible resonance forms for the dialkyldithiocarbamate

ferrocene complexes,41 as shown below.

so
5 R \ e/R
\\ _N/ H IC=N\
ch/ \R PCS R

PC = ferrocenyl backbone.

103

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Figure 12. 250 MHz

104

 

 

 

 

 

IMU. a

Ill . [1 l
s 4 3 2

1H NMR spectrum of g9, R = SCSNMe

2.

105

 

 

 

 

150 100 50

Figure 13. Gated decoupled 13C NMR of _6_6_.

 

 

106

The second resonance form introduces a degree of double bond character
into the carbon—nitrogen bond which prevents free rotation around the C-N
bond. The 1H NMR and 13C NMR data in Table 17 and Table 18 show that
two separate signals were observed for the N ,N-dialkyl group of the diethyldithio-
carbamate ferrocene derivative, g, at room temperature, but the dimethyldithio-
carbamateferrocene derivative, gig, are observed only at a lower temperature
(12°C). When the temperature is raised, the two N,N-dialkyl signals coalesce,
and as the fast exchange limit is approached they sharpen to a single peak.
The protons on the cyclopentadienyl rings show no such variation with temperature.
The behavior of the alkyl protons is due to the restricted rotation around
the carbamate C-N bond and a rough approximation of the barrier to rotation
about this bond has been determined. NMR parameters, rate constants and
an approximate value of the barrier to rotation in compounds §§_, and _61, are
given in Table 19. The rate constant, kc, at the coalescence temperature,
Tc, was determined from the peak separation, AV, at slow exchange by using
the equation117 kc = "AV/(2)1”. An approximate rotational free energy
barrier was obtained from the Eyring equation:

AG* = 2.303RT[10.3-log(Kc/TC)].

The values of the rotational barriers are 15.36 and 15.81 kcal/mol for compounds
g and 6_.7_, respectively. These AG values, though of fairly narrow range,
reveal that the rotational barrier of the NEt2 in Q is higher than that of N M82
in fig. This is to be expected since the diethylamino group is more sterically
hindered than the dimethylamino group in a 1,2-disubstituted cyclopentadienyl
ring.

Hollaway118 has determined'rotational barriers about the carbamate

107

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

1

Figure 14. Variable-temperature H NMR spectra of _6_6_, R = SCSNMez.

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0:89:33:uoEoEEaEEoE 5 0:30.550; 353‘ 0:30.20..—
ou on. on. m on. v
@oso nzo©mdo 21© .6 a

«oEZm no 92. c an ado E; a

70.3 S

75.0 II
75-7©—SCNMe2
Fe

110

83.9
Fe NM92

69.4 5

75.0 II
71.3 SCNMe2
7643 884
NMez

Fe

 

CI)

Figure 16. Assignment of ring carbons in some ferrocenyl carbamate

derivatives .

111

C-N bond in a series of N ,N-dialkyldithiocarbamate esters. Activation energies
of 10 to 12 kcal/mol suggested that an appreciable amount of C-N double bond
character Was present. Hollaway was able to correlate the C-N double bond
character with the "thioureide" band between 1489 and 1498 cm‘1 in the infrared
region. The "thioureide" band, which has been assigned to the partial double
bond character in the carbon-nitrogen bond, was observed at 1495 cm‘1 for

the chiral dimethylaminoethyldimethyldithio carbamate derivative _6_§_, and

1489 cm‘1 for the dimethylaminoethyldiethyldithio carbamate derivative _61.

The variable temperature 1H NMR spectrum for the chiral dimethylaminoethyl-

dimethyldithio carbamate derivative, Q, is shown in Figure 14.

D. Catalytic Applications of Complexes

1. Asymmetric Grignard Cross-Coupling Reactions

Asymmetric carbon-carbon bond-forming reactions are of great significance
for the synthesis of optically active compounds, and the use of chiral transition—
metal catalysts for such reactions has recently attracted considerable attention
due to a number of advantages of catalytic asymmetric synthesis.120 The
first report on asymmetric Grignard cross-coupling appeared in 1973, where
2,3—o-isoproylidene—2,3—dihydroxyl-1,4-bis(diphenylphosphino)butane ( DIO P)
was used as a chiral ligand on a nickel catalyst and 7-16% of the products
were obtained in the reaction of (l-phenylethyl)magnesium chloride. Since
the first report in 1975 that Pd complexes catalyze the coupling of Grignard
reagents with organic halides,122 the method has been used with a variety
of Grignard reagents and halogenated species. Kumada and co-workers123
has examined various types of chiral ferrocenylphosphine ligands for the nickel-
or palladium-catalyzed reaction of (l-phenylethylFmagnesium chloride with

vinyl bromide and found that the ferrocene planar chirality played an important

112

role rather than the carbon centered chirality on the side chain of the ferocene
and concluded that the asymmetric induction on the coupling product was
mainly determined by transmetallation of the alkyl group from the Grignard
reagent to the transition-metal catalyst and the most important intermediate

of the reaction was the diastereomeric transition state shown below.

 

 

 

The development of such transition metal catalysis depends largely on
the availability of suitable ligating compounds. Up to now only chiral phosphines
or phosphineamine combinations have provided satisfactory
results.67,124 This is a severe limitation for the synthesis of phosphines is
not simple and the derived ligands, once obtained, are often sensitive, especially
to oxidation by air.

These condiderations induced us to investigate application of our new
I chiral ferrocenylthioether compounds as potential ligands. While in the process
of this work, Kellogg and his co--workers,69 reported the asymmetric Grignard
cross-coupling reactions of l-phenylethylmagnesium chloride with vinyl bromide

by using nickel catalyzed bi- and polydentate sulfide ligands and obtained good

Asymmetric Grignard Cross—Coupling Reactions
Using Chiral Thioether Complexes

Catalyst

L33 L3 .3 Lg
=1 :1 21 23 :1
u
"U
3‘

II
..b
l
C)
n—n
l
"U
3'

a Reference 69

113

Table 20

Chemical Yield(%)

97.5
95.0
96.0
96.0
94.5

100

e.e.(%)

26.0
22.3
18.2
25.5
16.5

16.9

Configuration

114

chemical yield but poor enantiomeric purity (0.8-16.9% e.e.).
The new chiral ferrocenylaminethioether palladium complexes, _58, fl,

£2181, was tested for asymmetric Grignard cross—coupling reactions represented

below
on. OK:
' 1
P1101101 + ClMgClh cascaz 5219131., PhCllCHz cn=cnz
BtzO > 95%
run

The results are shown in Table 20. Since the optical rotation of the coupling
product 4-phenyl—1-pentene was strongly affected by small impurities70 and
in addition recemization of products always occur, it was difficult to determine
the optical purity by use of a polarimeter. The alkene was converted into
the methylester, the enantiomeric purity of which was determined by 1H NMR

spectroscopy in the presence of a chiral shift reagent, Eu(dcm)3.82 The chemical

shift ( 6), and the enantiomeric shift difference ( AA5 ) depend on the concentration
of the chiral shift reagent and the temperature at a constant concentration

of the substrate (0.5 M) in CDCl3 as shown in Figures 17 and 18 respectively.

At room temperature the 1H NMR signal of the methyl protons of the methyl

ester is a singlet when no chiral shift reagent is present. Upon addition of

the shift reagent the signal separates into two distinct singlets. The signal

shifted downfield and AAA increased as the concentration of the chiral shift
reagent increased. When the concentration of the chiral shift reagent was

0.27 M, AAG was large enough for the determination of the enantiomeric

excess (e.e.) (see Figure 17 and 18). Kumada125 had reported that the methyl

115

i“:

 

 

 

CH3
PthCI CHz-CHCHzMgBr
CH
a: 33'
M92
f / .3“
quz ' E/ \Cth
R 1
CH,

 

E'S.
Scheme16 Proposed Mechonnsm for Grignard

Cross Coupling Reocnon.

8.4x I .r .ér' ...-man...
a I

Pulm‘hfi-‘afi

116

.z-.o .uv ecu .zw~.o
“UV .zac.o any .zc.o ..V a. naauevau co use» ecu .mzp\m_uau a. :m.c m_ «Lacuna omega
:. muscumnam mo eo.uaau:uu=ou web .masuuvau .ucmmauc um.gm _oc_;u Co m:o_uagu=oucou
9.33.85 be 8:32.. 2.» 5 323.5 3.23-,” 359-Amy 23 a: .3 shown... «:2 zfl .5953...

 

 

 

 

 

 

 

 

 

 

 

 

o p s .zaa
_ . i i . _ . . . . . . ... . .14.
a
«i _#=fia\.
-1A -.4
. . .4 ..4 -.J _

 

mm

117

 

 

 

~3o°c

 

 

 

 

 

 

 

 

 

  

.5,’ 27°C

Figure 18- The magnitudes ofAA5increase for methyl 3-pheny1butyrate with
decreasing temperature in the presence of chirai shift reagent.

Eu(dcm)3. The concentration of substrate and chiral shift reag-
ent in Clxia/THS are 0.5 and 0.27 M. respectively.

118

signal of (_S_)-methy1 3—phenyl butyrate appears at a higher field than that of
the _13_ enantiomer.

The chiral ferrocenylamine thioether complexes with Pd, Q, g, fl-fi,
catalyzed formation of 4-phenyl-1-pentene from l—phenyl-l-chloroethane
and allylmagnesium chloride at 0° in high yield 095%). The resulting configura-
tion in all cases were _S_ (see Table 20). The enantiomeric excess (e.e) range
from 16.5 to 26.0 e.e (_S_) and is much higher than those reported by Kellogg.69
The Grignard cross-coupling reaction mechanism using phosphine-amine-palladium
complex was postulated by Kumada.123 Based on that we have also proposed
a mechanism for the chiral thioether-palladium catalyzed reaction (Scheme
16). It should be noted from our results that the planar chirality played an
important role rather than the carbon centered chirality of the side chain
of the ferrocenyl ligand in the asymmetric induction. Thus the configuration
of the coupling product was consistent with the planar chirality of the chiral

ferrocenylaminethioether-Pd catalysts.

2. Selective Hydrogenation of Conjugated Dienes to Alkenes
Hydrogenation by homogeneous catalysts is well-developed.133 Of the
many known complexes, those of Group VIII metals with amines and sulfides
have been used with varying degrees of success. In 1967 PtC12(SPh2)2 was
found to be selective for the hydrogenation of dienes to monoenes in the presence
of SnC12.134 Treatment of PdClg or NadeCI4 with tertiary amines resulted
in an active selective catalyst.135 The same was true of PdClZ when treated
with 2,2'—bipyridine and NaBH4.136 Palladium chloride and thioethers gave
complexes which upon reduction by diisobutylaluminum hydride, were selective
catalysts.”7 The thioetherrhodium complex, RhClg(SEt2)3 hydrogenates

maleic acid, provided maleic acid is present in excess.138’141

119

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HYDROGEN PRESSURE (psi)

80 «-

60 4i

I

40*

 

120

I4!-
«P

REACTION TIME (h)

Figure 19: Selective Hydrogenation of 1.3-cyclooctadiene in Acetone at 27°C

and 67 psi Using Complex §_§. R = Me

HYDROGEN PRESSURE (mi)

30...

60 au-

404

20‘

121

 

 

 

 

% i i #1
0 5 15 25
REACTION TIME (h)
Figure '20: Selective Hydrogenation of 1.3-cyclooctadiene in Acetone at 27°C

and 67 psi Using :32, R = Ph

122

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In view of the selective hydrogenation of thioether-palladium
complexes,52’138 we have carried out selective hydrogenation of conjugated
dienes to alkenes using ferrocenylamine thioether-palladium complexes 58,

62-64. Our results have previously reported that hydrogenations using thioether-
palladium complex failed if reducing agents were added.52 Hydrogenation

of 1,3-cyclooctadiene proceeded conveniently in acetone at 67 psi (see Figure

18). This is a homogeneous reaction system without H20 or reducing agents

and reaction proceeds at a useful rate (up to 462 mol/mol Pd.Hr) to afford

a high conversion of nearly 9696. As time passed the red solution became brown
but remained homogeneous. Most of the product at the end'of reaction was
cyclooctene, but some cyclooctane was present. The compounds present after
each of the hydrogenation reactions were 1,3-cyclooctadiene, cyclooctene

and cyclooctane. The (diene + monoene):a1kane ratio was determined by gas
chromatography, the two peaks being separated typically by more than 0.8
minutes. The ratio of the diene to monoene was determined by 1H NMR, as
illustrated in Figure 21. The central olefinic protons of the diene appear near

5.8 ppm while the outer protons appear around 5.6 ppm. The olefinic protons

of the monoene appear around 5.6 ppm. The ratio of monoene to diene is therefore

given by;

Monoene A55 - A5.3

 

Diene - A53

The selective hydrogenations of 1,3-cyclooctadiene in acetone at 27°C and
67 psi initial hydrogen pressure using thioether-palladium complexes _5_§_ and
fig as catalysts are shown in Figure 19 and Figure 20 respectively. Table 21
shows that the ratio of products (selectivity) and initial turnover rates depend

on the nature of the alkyl group present in the catalyst. Steric crowding rather

124

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45>Cw0
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FR:
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\l/Pd\ ’ - M92N\ /CI
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FFC /p:d\
I
Pd 1.0_§
/ \ .
H v

Scheme 17. Proposed Mechanisms for Homogeneous Selective Hydrogenation
of 1,3-cyclooctadiene via a 4-coordinate intermediate.
Fc- - Z-alkylthioetherferrocenylderivative.

126

than inductive effects of the aryl and alkyl groups present in the catalyst,
favor selective hydrogenation.

The effect of solvents on the hydrogenation of 1,3-cyclohexadiene at
room temperature is given in Table 22. The catalyst and substrate are soluble
in 0014. However, the solution is catalytically inactive since H2 is unable
to add oxidatively to Pd. When the catalyst and substrate are dissolved in
acetone, acetone replaces the thioether and coordinates to Pd, and thus induces
hydrogenation. In a mixed solvent of actone and C014, the hydrogenation
turnover rate decreases but the selectivity increases slightly, indicating that

proper choice of solvent is essential in the selective hydrogenation process.

IV. APPENDIX

 

 

 

 

 

 

 

 

 

l L l L A
6 5 4 3 3 1 0
complex.

Figure 3. 250 MHz 1H NMR spectrum of §§5 PdCl2

 

 

 

LgAA . L A

'1]

9 “:0 MHz 1H NMR Spectrum 3f fig, R=Me.

127

128

 

 

 

a“; ‘

 

 

 

 

 

 

 

 

 

.  g . l k
.mw ... Mmmmmmm

80 SO 30 0

13

Figure 23. Gated decoupled C NMR of fig, R=Me.

129

 

[I

 

 

 

J}
an
m
a
a
81

PPM

Figure 24; 250 MHz 1H NMR Spectra of g, R = Me

130

C11 A

 

Figure 2 5: Structure of Dichloroll-dimethylaminomethyl-Z-t—
butylthioferrocenyllpalladiulnfll).

 

_ - -«'n."l Jfi
l
I

 

V. REFERENCES

 

10.

11.

12.

13.

14.

15.

16.

17.

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