Advances in organometallic chemistry. / Volume 5

386 Pages·1967·14.956 MB·English

by  F Gordon A Stone, Robert West

ADVISORY BOARD:
H. J. EMELEUS HENR Y GI LMA N
CONTRIBUTORS TO THIS VOLUME
E. W. Abel
A. Aguil6
D. A. Armitage
Melvyn R. Churchill
M. F. Lappert
Ronald Mason
Rokuro Okawara
B. Prokai
John S. Thayer
Masanori Wada
Robert West
Advances in
ORGANOME TALLIC
CHEMISTRY
EDITED BY
F. G. A. STONE ROBERT WEST
DEPARTMENT OF INORGANIC CHEMISTRY DEPARTMENT OF CHEMISTRY
SCHOOL OF CHEMISTRY UNIVERSITY OF WISCONSIN
THE UNIVERSITY MADISON, WISCONSIN
BRISTOL. ENGLAND
VOLUME 5
I967
ACADEMIC PRESS New York 0 London
COPYRIGH@T 1967, BY ACADEMIPCR ESSIN C.
ALL RIGHTS RESERVED.
NO PART OF THIS BOOK MAY BE REPRODUCED IN ANY FORM,
BY PHOTOSTAT, MICROFILM, OR ANY OTHER MEANS, WITHOUT
WRITTEN PERMISSION FROM THE PUBLISHERS.
ACADEMIC PRESS INC.
111 Fifth Avenue. New York, New York 10003
United Kingdom Edition published by
ACADEMIC PRESS INC. (LONDON) LTD.
Berkeley Square House, London, W.l
LIBRAROYF CONGRESCSA TALOCGA RDN UMBE6R4-:1 6030
PRINTED IN THE UNITED STATES OF AMERICA
List of Contributors
Numbers in parentheses indicate the pages on which the authors' contributions begin.
E. W. ABEL( I), Department. of Inorganic Chemistry, The University, Bristol,
England
A. AGUIL(~32 1)) Celanese Chemical Company, Technical Center, Corpus
Christi, Texas
D. A. ARMITAG(EI) , Department of Inorganic Chemistry, The University,
Bra'stol, England
MELWNR . CHURCHI(L9L3 ))D epartment of Chemistry, Harvmd University,
Cambridge, Massachusetts
M. F. LAPPERT(2 25)) The Chemical Laboratory, University of Sussex,
Brighton, England
RONALDM ASON( 93)) Department of Chemistry, University of Shefield,
England
ROKUROOK AWAR(1A3 7))D epartment of Applied Chemistry,O saka University,
Higashinoda, Miyakojima, Osaka, Japan
B. PROKA(I2 25))C hemistry Department, Massachusetts Institute of Tech-
nology, Cambridge, Massachusetts
JOHN S. THAYE(R1 69))D epartment of Chemistry, Illinois Institute of Tech-
nology, Chicago, Illinois
MASANOWRIA DA(1 37))D epartment of Applied Chemistry, Osaka University,
Higashinoda, Miyakojima, Osaka, Japan
ROBERTW EST (169)) Department of Chemistry, University of Wisconsin,
Madison, Wisconsin
1 Present address: Department of Chemistry, University College, London, England.
2 Present address: Department of Chemistry, University of Cincinnati, Cincinnati, Ohio.
Organosulfur Derivatives of Silicon,
Germanium, Tin, and Lead
E. W. ABEL and D. A. ARMITAGE
Deportment of Inorganic Chemistry,
The University,
Bristol, England
I. Introduction . . . . 2
. . .
11. Synthetic Methods . 3
.
A. From Halides . 3
B. From Organometallic Oxygen Compounds . . 10
.
C. From Organometallic Nitrogen and Phosphorus Compounds 13
. . .
D. Cleavage of Metal-Carbon Bonds . 1 4
. . . .
E. Fission of Metal-Metal Bonds 15
F. From Organometallic Hydrides . . 16
G. Synthesis of Rs MIv SMI . . 18
H. Reactions of Rs MIv XMI (X = Sor Se) . . 19
I. By Heating Group IV Metal-Sulfur Compounds . . . 21
J. Miscellaneous . . . . 22
111. Chemical Properties . . . . 23
A. Heat and Ultraviolet Light . . 23
. .
B. Oxidation 23
. . . . .
C. Reduction 24
D. Reactions with Protonic Materials . . . . 24
E. Reactions with Covalent Halides . . . 27
F. Reactions with Organolithium Compounds . . 34
G. Reactions with Metal Salts . . 35
. .
H. Miscellaneous Reactions 37
IV. Physical Properties . . . . 38
A. X-Ray Diffraction . . . . 38
. . .
B. Electron and Neutron Diffraction 39
C. Infrared and Raman Spectroscopy . . . 40
D. Nuclear Magnetic Resonance Spectroscopy . . 41
E. Dipole Moments . . 42
F. BondParachors . . . . 43
. . .
G. Magnetic Susceptibility . 4 4
H. Molar Refractivities . . . . 4 4
V. Theoretical Considerations . . . . 44
. . .
A. Bond Strength . 4 4
B. Electronegativity . . . . 45
. . .
C. n Bonding in Silicon Compounds 45
D. The Group IV Metal-Sulfur Compounds . . . 47
2 E. W. ABEL and D. A. ARMITAGE
. . . . . . .
VI. Industrial Interests 49
A. Silicon and Germanium . . 49
. .
B. Tin 49
C. Lead . . 50
VII. Appendix: Tabular Survey (Tables 1-12) . . 51
. . . . . . . .
References. 83
I
INTRODUCTION
Whereas organotin and organolead compounds of sulfur were reported as
early as 1860 (121, 136, 137), the corresponding germanium compounds
were first made in 1932 (42),a nd rather surprisingly, organosilicon sulfides
were not synthesized until 1950 (71).
It is pertinent here to point out some of the restrictions we have imposed
on the scope of this article. We shall consider only the bivalent sulfur com-
pounds of the tetravalent Group IV elements, thus excluding such extensive
fields as the lead(I1) mercaptides (182) and organometallic salts of sulfur
oxyacids. No mention will be made of coordinated sulfur compounds of
these elements, and isothiocyanates will only be considered where they
illustrate a property of a sulfur compound under review. Silyl and germyl
compounds and the thiohalogeno derivatives of the Group IV elements
only appear where necessary for comparison purposes. The chemistry of
the selenium and tellurium analogs of the sulfur compounds under con-
sideration are fully reviewed.
Nomenclature is founded on the presently accepted convention of the
tetravalent silicon and germanium compounds being silane and germane,
with the tin and lead compounds based on the name of the metal (109).
Thus, for example, the names of (CHJ2Si(SC2HS)2a nd (CH3)2Sn(SC2Hs)2
are, respectively, bis(ethy1thio)dimethylsilane and bis(ethy1thio)dimethyl-
tin.
A number of excellent reviews exist on various aspects of the organic
chemistry of the Group IV elements, and the reader is referred to these for
wider discussion of the general properties of these materials: silicon (29,
73, 74, 251, 153,228);g ermanium (111, 277, 184, 285,228);t in (109, 148,
149, 161, 182,228,235);le ad (142,254).
Derivatives of Silicon, Germanium, Tin, and Lead 3
II
SYNTHETIC METHODS
A. From Halides
1. Amine Method
The condensation of thiols and halogenosilanes, with the direct elimina-
tion of hydrogen halide, has been reported to give a very small yield of a
silicon-sulfur compound (114). The use of amine as a base for the removal
of the hydrogen halide has, however, proved one of the most general'
methods available for the formation of sulfur bonds to silicon, germanium,
tin, and lead.
This reaction has sometimes been noted to be reversible at elevated
temperatures, and linear alkylthio derivatives of silicon (257), germanium
(69, 107),t in (69),a nd lead (69)h ave all been prepared by this method.
RnMX4-n+ (4-n)R'SH+(4-n)R"sN + RnM(SR)4-n+(4-n)RX3NHX (1)
An analogous reaction involves the initial formation of the bis(pyridine)-
metal tetrahalide complex which is subsequently treated with further
pyridine in the presence of thiol (I, 107).
+ +
MC14(CsHsN)z 4RSH 2CsHsN + M(SR)4+ 4CsHsNHC1 (2)
M=Si an&Ge
The use of hexamethyldisilazane as the base [see Eq. (l)] has been
successful in the preparation of allylthiotrimethylsilane (P71), but the
analogous reaction with n-butanethiol is reported to yield no silicon-sulfur
derivative (140).
Utilization of dithiols or difunctional systems in these reactions can lead
either to linear or cyclic compounds. Thus the interaction of bromotri-
phenylgermane and chlorotriphenyllead with dithiols yielded the linear
compounds (C6H5)3MSRSM(C6H5)3w,h ere R is
+
Z(CeHs)aMX+HSRSH 2CsHsN + (CsHs)3MSRSM(CaHs)3 (3)
The earliest type of cyclic compound prepared by this method was from
-
4 E. W. ABEL and D. A. ARMITAGE
the interaction of ethane-1,Zdithiol and the dialkyl or diary1 metal dihalides
(69,249,P 55).
+
RzMXz $HS(CHz)zSH 2R3N -+ CHZ-S-M(RZ)SCHZ (4)
(1)
M = Si, Ge, Sn, and Pb
Variation of the difunctional thiol has resulted in the synthesis of a
variety of novel heterocyclic compounds: (11) (243,250);( 111) (251);( IV)
(247);( V) (248);( VI) (243, 252); (VII) (246, 252). Using the dichloride
ClCH2M(CH3)2CI( M = Si and Ge) has given a further modification to the
ring systems produced: (VIII) (245);( IX) (245);( X) (244, 248). The two
spirans (XI) and (XII) have also been prepared from the thiols and ger-
manium tetrachloride in the presence of pyridine (69).
0
The reaction of hydrogen sulfide under similar conditions resembles
that of the thiols, but leads to a wider variety of products. The triphenyl
Derivatives of Silicon, Germanium, Tin, and Lead 5
H'zC- CHz
s '
HzC
\ I
M Rz
HzC- CHz
I \
S'G€?
/ /
s s
1 1
HK-CHz
halides of silicon (83) and germanium (69) react to give the thiol, whereas
analogous tin and lead halides yield the hexaphenyldimetal sulfides.
+
(CaHs)3MX+HzS+CsHsN -+ (CaH&MSH C5HiiN.HX (5)
M=Si, X=CI; M=Ge, X=Br
The germanium compound is reported to smell of hydrogen sulfide in the
presence of moisture, just as triphenylmethanethiol does (236).
The l-bromo-1,3-disilapropanes[ see Eq. (6)] react in a similar way to
give the silanethioIs (158).
+ + +
RsSiCHzSiRzBr HzS C5H5N + R3SiCHzSiRzSH C5H5N'HX (6)
R= CH3 and C2H5
These thiols reacted with further bromide and pyridine to give the di-
silthianes (R3SiCH2SiR2)2Ss, uch compounds being normally prepared
directly from the halide and hydrogen sulfide.
Thus, halides of the type R3MX react with hydrogen sulfide according
to Eq. (7) to give the substituted disilithianes (63, 158) and digermthianes
(7).
2RsMX+HzS+2R'sN (R3M)zS +2R'3N*HX (7)
-+
M=Si and Ge
Dihalides of silicon react in a similar way to produce compounds of formula
R2SiS.
+ +
RzSiXz +HzS 2R'sN -+ RzSiS 2R'sNHX (8)
These materials have been isolated as dimers (XIII) (63, 82, 154) and
trimers (XIV) (154, 163, P54).
6 E. W. ABEL and D. A. ARMITAGE
The compound (C6Hll)ZPbSh as also been obtained by this route (96).
The analogous reactions of hydrogen sulfide and base with the trihalides
in general produce the compounds (RSi)&. The compounds are claimed
to be dimeric (82, 83).
+ + +
4RSiCls 6HzS 12R3’N [(RSi)zS& 12RdNHCl (9)
-+
A deficiency of pyridine has given the compound (XV) (82) analogous to
those produced from dihalides ; it should possess separable geometrical
isomers.
It reacts further with hydrogen sulfide and pyridine to produce
(TZ-C~H,S~()8~2S) a~n d gives the slender evidence quoted that these tri-
sulfides have structure (XVI) and not (XVII).
R
The ring systems (XVIII) (211), (XIX) (237),( XX) (30)a nd (XXI) (30),
have been produced by the reactions recorded in Eqs. (10)-(13), respec-
tively.
+
2ClCHzSi(CHs)zCl+ 2HzS 4(CzHs)aN -+ (XVIII) (10)
+
2Cl(CH3)2SiSi(CHs)zCl+2 H2S 4CsHsN -+ (XIX) (11)
[(CICH~)~S~O]ZS~(CH~f)2ZC+sHHZsNS -+ (XX) (12)
+
2Cl(CHs)zSiOSi(CHs)zCl+ 2HzS 4CsHsN -+ (XXI) (13)