The Chemistry of Organic Germanium, Tin and Lead Compounds. Volume 2
Edited by Zvi Rappoport
Copyright  2002 John Wiley & Sons, Ltd.
ISBN: 0-471-49738-X

The chemistry of
organic germanium, tin
and lead compounds


THE CHEMISTRY OF FUNCTIONAL GROUPS
A series of advanced treatises founded by Professor
Saul Patai and under the general editorship of Professor Zvi Rappoport
The chemistry of alkenes (2 volumes)
The chemistry of the carbonyl group (2 volumes)
The chemistry of the ether linkage
The chemistry of the amino group
The chemistry of the nitro and nitroso groups (2 parts)
The chemistry of carboxylic acids and esters
The chemistry of the carbon–nitrogen double bond
The chemistry of amides
The chemistry of the cyano group
The chemistry of the hydroxyl group (2 parts)
The chemistry of the azido group
The chemistry of acyl halides
The chemistry of the carbon–halogen bond (2 parts)
The chemistry of the quinonoid compounds (2 volumes, 4 parts)
The chemistry of the thiol group (2 parts)
The chemistry of the hydrazo, azo and azoxy groups (2 volumes, 3 parts)
The chemistry of amidines and imidates (2 volumes)
The chemistry of cyanates and their thio derivatives (2 parts)

The chemistry of diazonium and diazo groups (2 parts)
The chemistry of the carbon–carbon triple bond (2 parts)
The chemistry of ketenes, allenes and related compounds (2 parts)
The chemistry of the sulphonium group (2 parts)
Supplement A: The chemistry of double-bonded functional groups (3 volumes, 6 parts)
Supplement B: The chemistry of acid derivatives (2 volumes, 4 parts)
Supplement C: The chemistry of triple-bonded functional groups (2 volumes, 3 parts)
Supplement D: The chemistry of halides, pseudo-halides and azides (2 volumes, 4 parts)
Supplement E: The chemistry of ethers, crown ethers, hydroxyl groups and their sulphur analogues (2
volumes, 3 parts)
Supplement F: The chemistry of amino, nitroso and nitro compounds and their derivatives
(2 volumes, 4 parts)
The chemistry of the metal–carbon bond (5 volumes)
The chemistry of peroxides
The chemistry of organic selenium and tellurium compounds (2 volumes)
The chemistry of the cyclopropyl group (2 volumes, 3 parts)
The chemistry of sulphones and sulphoxides
The chemistry of organic silicon compounds (3 volumes, 6 parts)
The chemistry of enones (2 parts)
The chemistry of sulphinic acids, esters and their derivatives
The chemistry of sulphenic acids and their derivatives
The chemistry of enols
The chemistry of organophosphorus compounds (4 volumes)
The chemistry of sulphonic acids, esters and their derivatives
The chemistry of alkanes and cycloalkanes
Supplement S: The chemistry of sulphur-containing functional groups
The chemistry of organic arsenic, antimony and bismuth compounds
The chemistry of enamines (2 parts)
The chemistry of organic germanium, tin and lead compounds (2 volumes, 3 parts)
The chemistry of dienes and polyenes (2 volumes)

The chemistry of organic derivatives of gold and silver
UPDATES
The chemistry of ˛-haloketones, ˛-haloaldehydes and ˛-haloimines
Nitrones, nitronates and nitroxides
Crown ethers and analogs
Cyclopropane derived reactive intermediates
Synthesis of carboxylic acids, esters and their derivatives
The silicon–heteroatom bond
Synthesis of lactones and lactams
Syntheses of sulphones, sulphoxides and cyclic sulphides
Patai’s 1992 guide to the chemistry of functional groups — Saul Patai

C Ge, C Sn, C Pb


The chemistry of
organic germanium, tin
and lead compounds
Volume 2

Edited by
ZVI RAPPOPORT
The Hebrew University, Jerusalem

2002

An Interscience Publication


Copyright  2002


John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester,
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Library of Congress Cataloging-in-Publication Data
The chemistry of organo-germanium, tin, and lead compounds / edited by Zvi Rappoport
and Yitzhak Apeloig.

p. cm. — (Chemistry of functional groups)
Includes bibliographical references and index.
ISBN 0-471-49738-X (v. 2 : alk. paper)
1. Organogermanium compounds. 2. Organotin compounds. 3. Organolead compounds.
I. Rappoport, Zvi. II. Apeloig, Yitzhak. III. Series.
QD412.G5 C49 2001
547 .05684–dc21
2001026197
British Library Cataloguing in Publication Data
A catalogue record for this book is available from the British Library
ISBN 0-471-49738-X
Typeset in 9/10pt Times by Laserwords Private Limited, Chennai, India
Printed and bound in Great Britain by Biddles Ltd, Guildford, Surrey
This book is printed on acid-free paper responsibly manufactured from sustainable forestry
in which at least two trees are planted for each one used for paper production.


Dedicated to
the memory of

Nahum
and

Zeev


Contributing authors
Klavdiya A. Abzaeva

Yuri I. Baukov


Sergey E. Boganov

Michael W. Carland
Annie Castel

Marvin Charton

Alexey N. Egorochkin

Mikhail P. Egorov

Valery I. Faustov

Eric Fouquet

Gernot Frenking
Inga Ganzer
Ionel Haiduc

A. E. Favorsky Institute of Chemistry, Siberian Branch of
the Russian Academy of Sciences, 1 Favorsky Str.,
664033 Irkutsk, Russia
Department of General and Bioorganic Chemistry,
Russian State Medical University, 1 Ostrovityanov St,
117997 Moscow, Russia
N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences, Leninsky prospect, 47,
119991 Moscow, Russian Federation
School of Chemistry, The University of Melbourne,

Victoria, Australia, 3010
Laboratoire d’H´et´erochimie Fondamentale et Appliqu´ee,
UMR 5069 du CNRS, Universit´e Paul Sabatier, 31062
Toulouse cedex, France
Chemistry Department, School of Liberal Arts and
Sciences, Pratt Institute, Brooklyn, New York 11205,
USA
G. A. Razuvaev Institute of Metallorganic Chemistry of
the Russian Academy of Sciences, 49 Tropinin Str.,
603950 Nizhny Novgorod, Russia
N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences, Leninsky prospect, 47,
119991 Moscow, Russian Federation
N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences, Leninsky prospect, 47,
119991 Moscow, Russian Federation
Laboratoire de Chimie Organique et Organom´etallique,
Universit´e Bordeaux I, 351, Cours de la Liberation,
33405 Talence Cedex, France
Fachbereich Chemie, Philipps-Universităat Marburg,
Hans-Meerwein-Strasse, D-35032 Marburg, Germany
Fachbereich Chemie, Philipps-Universităat Marburg,
Hans-Meerwein-Strasse, D-35032 Marburg, Germany
Department of Chemistry, University of Texas at El Paso,
El Paso, Texas 79968, USA

vii


viii

Michael Hartmann
Luba Ignatovich
Klaus Jurkschat
ă
Thomas M. Klapotke

Karl W. Klinkhammer
Stanislav Kolesnikov

Alexander I. Kruppa
Vladimir Ya. Lee
Tatyana V. Leshina
Conor Long
Edmunds Lukevics
Heinrich Chr. Marsmann

Michael Mehring
Josef Michl
Oleg M. Nefedov

Renji Okazaki

Keith H. Pannell
Mary T. Pryce
Olga Pudova
ă
Claudia M. Rienacker

Contributing authors
Fachbereich Chemie, Philipps-Universităat Marburg,

Hans-Meerwein-Strasse, D-35032 Marburg, Germany
Latvian Institute of Organic Synthesis, Aizkraukles 21,
Riga, LV-1006 Latvia
Lehrstuhl făur Anorganische Chemie II der Universităat
Dortmund, D-44221 Dortmund, Germany
Department of Chemistry,
Ludwig-Maximilians-University Munich, Butenandtstr.
5-13 (Building D), D-81377 Munich, Germany
Institute for Inorganic Chemistry, University of Stuttgart,
Pfaffenwaldring 55, D-70569 Stuttgart, Germany
N. D. Zelinsky Institute of Organic Chemistry, Russian
Academy of Sciences, 47 Leninsky prospect, 119991
Moscow, Russian Federation
Institute of Chemical Kinetics and Combustion,
Novosibirsk-90, 630090 Russia
Department of Chemistry, University of Tsukuba,
Tsukuba, Ibaraki 305-8571, Japan
Institute of Chemical Kinetics and Combustion,
Novosibirsk-90, 630090 Russia
School of Chemical Sciences, Dublin City University,
Dublin 9, Ireland
Latvian Institute of Organic Synthesis, Aizkraukles 21,
Riga, LV-1006, Latvia
Universităat Paderborn, Fachbereich Chemie, Anorganische
Chemie, Warburger Straòe 100, D-30095 Paderborn,
Germany
Lehrstuhl făur Anorganische Chemie II der Universităat
Dortmund, D-44221 Dortmund, Germany
Department of Chemistry and Biochemistry, University of
Colorado, Boulder, CO 80309-0215, USA

N. D. Zelinsky Institute of Organic Chemistry, Russian
Academy of Sciences, 47 Leninsky prospect, 119991
Moscow, Russian Federation
Department of Chemical and Biological Sciences, Faculty
of Science, Japan Women’s University, 2-8-1 Mejirodai,
Bunkyo-ku, Tokyo 112–8681, Japan
Department of Chemistry, University of Texas at El Paso,
El Paso, Texas 79968, USA
School of Chemical Sciences, Dublin City University,
Dublin 9, Ireland
Latvian Institute of Organic Synthesis, Aizkraukles 21,
Riga, LV-1006, Latvia
Department of Chemistry,
Ludwig-Maximilians-University Munich, Butenandtstr.
5-13 (Building D), D-81377 Munich, Germany


Contributing authors
Jose´ M. Riveros
Pierre Riviere

Monique Riviere-Baudet

Carl H. Schiesser
Akira Sekiguchi
Hemant K. Sharma
Keiko Takashima
Stanislav N. Tandura

Marc B. Taraban

Norihiro Tokitoh
Frank Uhlig

Olga S. Volkova
Mikhail G. Voronkov

Ilya Zharov

ix

Institute of Chemistry, University of S˜ao Paulo, Caixa
Postal 26077, S˜ao Paulo, Brazil, CEP 05513-970
Laboratoire d’H´et´erochimie Fondamentale et Appliqu´ee,
UMR 5069 du CNRS, Universit´e Paul Sabatier, 31062
Toulouse cedex, France
Laboratoire d’H´et´erochimie Fondamentale et Appliqu´ee,
UMR 5069 du CNRS, Universit´e Paul Sabatier, 31062
Toulouse cedex, France
School of Chemistry, The University of Melbourne,
Victoria, Australia, 3010
Department of Chemistry, University of Tsukuba,
Tsukuba, Ibaraki 305-8571, Japan
Department of Chemistry, University of Texas at El Paso,
El Paso, Texas 79968, USA
Department of Chemistry, University of Londrina, Caixa
Postal 6001, Londrina, PR, Brazil, CEP 86051-970
N. D. Zelinsky Institute of Organic Chemistry, Russian
Academy of Sciences, 47 Leninsky prospect, 119991
Moscow, Russian Federation
Institute of Chemical Kinetics and Combustion,

Novosibirsk-90, 630090 Russia
Institute for Chemical Research, Kyoto University,
Gokasho, Uji, Kyoto 611-0011, Japan
Universităat Dortmund, Fachbereich Chemie, Anorganische
Chemie II, Otto-Hahn-Str. 6, D-44221 Dortmund,
Germany
Institute of Chemical Kinetics and Combustion,
Novosibirsk-90, 630090 Russia
A. E. Favorsky Institute of Chemistry, Siberian Branch of
the Russian Academy of Sciences, 1 Favorsky Str.,
664033 Irkutsk, Russia
Department of Chemistry and Biochemistry, University of
Colorado, Boulder, CO 80309-0215, USA


Foreword
The preceding volume on The Chemistry of Organic Germanium, Tin and Lead Compounds
in ‘The Chemistry of Functional Groups’ series (S. Patai, Ed.) appeared in 1995. The
appearance of the present two-part volume seven years later reflects the rapid growth of
the field.
The book covers two types of chapters. The majority are new chapters on topics which
were not covered in the previous volume. These include chapters on reaction mechanisms
involving the title organic derivatives, on reactive intermediates derived from them, like
cations and carbene analogs, on NMR spectra, and on gas phase and mass spectrometry of
organic germanium, tin and lead derivatives. There are chapters on their alkaline and alkaline earth metal compounds, on highly reactive multiply-bonded derivatives involving the
title elements and on their hypervalent compounds, their synthetic applications, biological
activities, polymers, cage compounds, unsaturated three membered ring derivatives and a
new germanium superacid.
The second group of chapters are updates or extensions of material included in previous
chapters. These include chapters on theory, on comparison of the derivatives of the three

metals, on new advances in structural and photochemistry and in substituent effects and
acidity, basicity and complex formation.
The volume opens with a new historical chapter on the genesis and evolution of organic
compounds of the three elements, written by one of the pioneers in the field. We hope
that such a historical background adds perspectives to those working both in the field and
outside it.
The contributing authors to the book come from nine countries including some from
Russia and Latvia who contributed several chapters. Part of the work in the field in these
countries was covered by articles in Russian which were frequently not easily available to
non-Russian readers. We now have many references including Chemical Abstract citations
which will facilitate access to these articles.
The literature coverage in the book is mostly up to mid- or late-2001.
One originally planned chapter on radical reactions was not delivered, but part of the
material can be found in another, more mechanistically oriented chapter.
This and the preceding volume should be regarded as part of a larger collection of books
which appeared in recent years in ‘The Chemistry of Functional Groups’ series and deal
with the chemistry of organic derivatives of the group 14 elements (excluding carbon).
These also include four parts on the chemistry of organic silicon compounds (Z. Rappoport
and Y. Apeloig, Eds., Vol. 2, parts 1–3, 1998 and Vol. 3, 2001) which follow two earlier
volumes (S. Patai and Z. Rappoport, Eds., 1989) and an update volume, The SiliconHeteroatom Bond (1991). The 136 chapters in the ten volumes cover extensively the
main aspects of the chemistry of this group in the periodic table. Some comparisons of
the derivatives of these groups appear both in the present and in earlier volumes.
This book was planned to be coedited by Prof. Y. Apeloig from the Technion in Haifa,
Israel, but he was elected to the presidency of his institute and was unable to proceed
xi


xii

Foreword


with the editing beyond its early stage. I want to thank him for the effort that he invested
and for his generous advice. I also want to thank the authors for their contributions.
I will be grateful to readers who draw my attention to mistakes in the present volume,
or mention omissions and new topics which deserve to be included in a future volume on
the chemistry of germanium, tin and lead compounds.

Jerusalem
April 2002

ZVI RAPPOPORT


The Chemistry of Functional Groups
Preface to the series
The series ‘The Chemistry of Functional Groups’ was originally planned to cover in
each volume all aspects of the chemistry of one of the important functional groups in
organic chemistry. The emphasis is laid on the preparation, properties and reactions of the
functional group treated and on the effects which it exerts both in the immediate vicinity
of the group in question and in the whole molecule.
A voluntary restriction on the treatment of the various functional groups in these
volumes is that material included in easily and generally available secondary or tertiary sources, such as Chemical Reviews, Quarterly Reviews, Organic Reactions, various
‘Advances’ and ‘Progress’ series and in textbooks (i.e. in books which are usually found
in the chemical libraries of most universities and research institutes), should not, as a rule,
be repeated in detail, unless it is necessary for the balanced treatment of the topic. Therefore each of the authors is asked not to give an encyclopaedic coverage of his subject,
but to concentrate on the most important recent developments and mainly on material that
has not been adequately covered by reviews or other secondary sources by the time of
writing of the chapter, and to address himself to a reader who is assumed to be at a fairly
advanced postgraduate level.
It is realized that no plan can be devised for a volume that would give a complete coverage of the field with no overlap between chapters, while at the same time preserving the

readability of the text. The Editors set themselves the goal of attaining reasonable coverage
with moderate overlap, with a minimum of cross-references between the chapters. In this
manner, sufficient freedom is given to the authors to produce readable quasi-monographic
chapters.
The general plan of each volume includes the following main sections:
(a) An introductory chapter deals with the general and theoretical aspects of the group.
(b) Chapters discuss the characterization and characteristics of the functional groups,
i.e. qualitative and quantitative methods of determination including chemical and physical
methods, MS, UV, IR, NMR, ESR and PES — as well as activating and directive effects
exerted by the group, and its basicity, acidity and complex-forming ability.
(c) One or more chapters deal with the formation of the functional group in question,
either from other groups already present in the molecule or by introducing the new group
directly or indirectly. This is usually followed by a description of the synthetic uses of
the group, including its reactions, transformations and rearrangements.
(d) Additional chapters deal with special topics such as electrochemistry, photochemistry, radiation chemistry, thermochemistry, syntheses and uses of isotopically labelled
compounds, as well as with biochemistry, pharmacology and toxicology. Whenever applicable, unique chapters relevant only to single functional groups are also included (e.g.
‘Polyethers’, ‘Tetraaminoethylenes’ or ‘Siloxanes’).
xiii


xiv

Preface to the series

This plan entails that the breadth, depth and thought-provoking nature of each chapter
will differ with the views and inclinations of the authors and the presentation will necessarily be somewhat uneven. Moreover, a serious problem is caused by authors who deliver
their manuscript late or not at all. In order to overcome this problem at least to some
extent, some volumes may be published without giving consideration to the originally
planned logical order of the chapters.
Since the beginning of the Series in 1964, two main developments have occurred.

The first of these is the publication of supplementary volumes which contain material
relating to several kindred functional groups (Supplements A, B, C, D, E, F and S). The
second ramification is the publication of a series of ‘Updates’, which contain in each
volume selected and related chapters, reprinted in the original form in which they were
published, together with an extensive updating of the subjects, if possible, by the authors
of the original chapters. A complete list of all above mentioned volumes published to
date will be found on the page opposite the inner title page of this book. Unfortunately,
the publication of the ‘Updates’ has been discontinued for economic reasons.
Advice or criticism regarding the plan and execution of this series will be welcomed
by the Editors.
The publication of this series would never have been started, let alone continued,
without the support of many persons in Israel and overseas, including colleagues, friends
and family. The efficient and patient co-operation of staff-members of the publisher also
rendered us invaluable aid. Our sincere thanks are due to all of them.
The Hebrew University
Jerusalem, Israel

SAUL PATAI
ZVI RAPPOPORT

Sadly, Saul Patai who founded ‘The Chemistry of Functional Groups’ series died in
1998, just after we started to work on the 100th volume of the series. As a long-term
collaborator and co-editor of many volumes of the series, I undertook the editorship and
I plan to continue editing the series along the same lines that served for the preceeding
volumes. I hope that the continuing series will be a living memorial to its founder.
The Hebrew University
Jerusalem, Israel
June 2002

ZVI RAPPOPORT



Contents
1 Genesis and evolution in the chemistry of organogermanium,
organotin and organolead compounds
Mikhail G. Voronkov and Klavdiya A. Abzaeva

1

2 Similarities and differences of organic compounds of germanium,
tin and lead
Mikhail G. Voronkov and Alexey N. Egorochkin

131

3 Theoretical studies of organic germanium, tin and lead
compounds
Inga Ganzer, Michael Hartmann and Gernot Frenking

169

4 Recent advances in structural chemistry of organic germanium, tin
and lead compounds
Karl W. Klinkhammer

283

5 Gas-phase chemistry and mass spectrometry of Ge-, Sn- and
Pb-containing compounds
Jos´e M. Riveros and Keiko Takashima


359

6 Further advances in germanium, tin and lead NMR
Heinrich Chr. Marsmann and Frank Uhlig

399

7 Recent advances in acidity, complexing, basicity and H-bonding
of organo germanium, tin and lead compounds
Claudia M. Rienăacker and Thomas M. Klapăotke

461

8 Structural effects on germanium, tin and lead compounds
Marvin Charton

537

9 Radical reaction mechanisms of and at organic germanium, tin
and lead
Marc B. Taraban, Olga S. Volkova, Alexander I. Kruppa and
Tatyana V. Leshina

579

10 Free and complexed R3 M+ cations (M = Ge, Sn, Pb)
Ilya Zharov and Josef Michl

633


11 Alkaline and alkaline earth metal-14 compounds: Preparation,
spectroscopy, structure and reactivity
Pierre Riviere, Annie Castel and Monique Riviere-Baudet

653

xv


xvi

Contents

12 Spectroscopic studies and quantum-chemical calculations of
short-lived germylenes, stannylenes and plumbylenes
Sergey E. Boganov, Mikhail P. Egorov, Valery I. Faustov and
Oleg M. Nefedov

749

13 Multiply bonded germanium, tin and lead compounds
Norihiro Tokitoh and Renji Okazaki

843

14 Unsaturated three-membered rings of heavier Group 14 elements
Vladimir Ya. Lee and Akira Sekiguchi

903


15 Cage compounds of heavier Group 14 elements
Akira Sekiguchi and Vladimir Ya. Lee

935

16 Hypervalent compounds of organic germanium, tin and lead
derivatives
Yuri I. Baukov and Stanislav N. Tandura

963

17 Transition metal complexes of germanium, tin and lead
Hemant K. Sharma, Ionel Haiduc and Keith H. Pannell

1241

18 Synthetic applications of organic germanium, tin and lead
compounds (excluding R3 MH)
Eric Fouquet

1333

19 Synthetic uses of R3 MH (M = Ge, Sn, Pb)
Michael W. Carland and Carl H. Schiesser

1401

20 Trichlorogermane, a new superacid in organic chemistry
Stanislav Kolesnikov, Stanislav N. Tandura and Oleg M.

Nefedov

1485

21 The photochemistry of organometallic compounds of germanium,
tin and lead
Conor Long and Mary T. Pryce

1521

22 Organometallic polymers of germanium, tin and lead
Klaus Jurkschat and Michael Mehring

1543

23 Biological activity of organogermanium compounds
Edmunds Lukevics and Luba Ignatovich

1653

24 Biological activity of organotin and organolead compounds
Edmunds Lukevics and Olga Pudova

1685

Author index

1715

Subject index


1877

Contents of Volume 1


List of abbreviations used
Ac
acac
Ad
AIBN
Alk
All
An
Ar

acetyl (MeCO)
acetylacetone
adamantyl
azoisobutyronitrile
alkyl
allyl
anisyl
aryl

Bn
Bz
Bu

benzyl

benzoyl (C6 H5 CO)
butyl (also t-Bu or But )

CD
CI
CIDNP
CNDO
Cp
Cp∗

circular dichroism
chemical ionization
chemically induced dynamic nuclear polarization
complete neglect of differential overlap
η5 -cyclopentadienyl
η5 -pentamethylcyclopentadienyl

DABCO
DBN
DBU
DIBAH
DME
DMF
DMSO

1,4-diazabicyclo[2.2.2]octane
1,5-diazabicyclo[4.3.0]non-5-ene
1,8-diazabicyclo[5.4.0]undec-7-ene
diisobutylaluminium hydride
1,2-dimethoxyethane

N,N-dimethylformamide
dimethyl sulphoxide

ee
EI
ESCA
ESR
Et
eV

enantiomeric excess
electron impact
electron spectroscopy for chemical analysis
electron spin resonance
ethyl
electron volt

xvii


xviii

List of abbreviations used

Fc
FD
FI
FT
Fu


ferrocenyl
field desorption
field ionization
Fourier transform
furyl(OC4 H3 )

GLC

gas liquid chromatography

Hex
c-Hex
HMPA
HOMO
HPLC

hexyl(C6 H13 )
cyclohexyl(c-C6 H11 )
hexamethylphosphortriamide
highest occupied molecular orbital
high performance liquid chromatography

iIp
IR
ICR

iso
ionization potential
infrared
ion cyclotron resonance


LAH
LCAO
LDA
LUMO

lithium aluminium hydride
linear combination of atomic orbitals
lithium diisopropylamide
lowest unoccupied molecular orbital

M
M
MCPBA
Me
MNDO
MS

metal
parent molecule
m-chloroperbenzoic acid
methyl
modified neglect of diatomic overlap
mass spectrum

n
Naph
NBS
NCS
NMR


normal
naphthyl
N-bromosuccinimide
N-chlorosuccinimide
nuclear magnetic resonance

Pc
Pen
Pip
Ph
ppm
Pr
PTC
Py, Pyr

phthalocyanine
pentyl(C5 H11 )
piperidyl(C5 H10 N)
phenyl
parts per million
propyl (also i-Pr or Pri )
phase transfer catalysis or phase transfer conditions
pyridyl (C5 H4 N)


List of abbreviations used
R
RT


any radical
room temperature

sSET
SOMO

secondary
single electron transfer
singly occupied molecular orbital

tTCNE
TFA
THF
Thi
TLC
TMEDA
TMS
Tol
Tos or Ts
Trityl

tertiary
tetracyanoethylene
trifluoroacetic acid
tetrahydrofuran
thienyl(SC4 H3 )
thin layer chromatography
tetramethylethylene diamine
trimethylsilyl or tetramethylsilane
tolyl(MeC6 H4 )

tosyl(p-toluenesulphonyl)
triphenylmethyl(Ph3 C)

Xyl

xylyl(Me2 C6 H3 )

xix

In addition, entries in the ‘List of Radical Names’ in IUPAC Nomenclature of Organic
Chemistry, 1979 Edition, Pergamon Press, Oxford, 1979, p. 305–322, will also be used
in their unabbreviated forms, both in the text and in formulae instead of explicitly drawn
structures.


The Chemistry of Organic Germanium, Tin and Lead Compounds. Volume 2
Edited by Zvi Rappoport
Copyright  2002 John Wiley & Sons, Ltd.
ISBN: 0-471-49738-X

CHAPTER 1

Genesis and evolution in the
chemistry of organogermanium,
organotin and organolead
compounds
MIKHAIL G. VORONKOV and KLAVDIYA A. ABZAEVA
A. E. Favorsky Institute of Chemistry, Siberian Branch of the Russian Academy of
Sciences, 1 Favorsky Str., 664033 Irkutsk, Russia
e-mail:


The task of science is to induce the future from the past
Heinrich Herz
I. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
II. ORGANOGERMANIUM COMPOUNDS . . . . . . . . . . . . . . . . . . . . . .
A. Re-flowering after Half a Century of Oblivion . . . . . . . . . . . . . . . . .
B. Organometallic Approaches to a C Ge and Ge Ge Bond . . . . . . . . .
C. Nonorganometallic Approaches to a C Ge Bond . . . . . . . . . . . . . . .
D. C Ge Bond Cleavage. Organylhalogermanes . . . . . . . . . . . . . . . . .
E. Compounds having a Ge H Bond . . . . . . . . . . . . . . . . . . . . . . . .
F. Organogermanium Chalcogen Derivatives . . . . . . . . . . . . . . . . . . . .
G. Organogermanium Pnicogen Derivatives . . . . . . . . . . . . . . . . . . . . .
H. Compounds having a Hypovalent and Hypervalent
Germanium Atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
I. Biological Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
III. ORGANOTIN COMPOUNDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
A. How it All Began . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
B. Direct Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
C. Organometallic Synthesis from Inorganic and Organic Tin Halides . . .
D. Organotin Hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
E. Organylhalostannanes. The C Sn Bond Cleavage . . . . . . . . . . . . . .

1

2
5
5
6
11
13

14
17
26
29
32
33
33
36
39
41
43


2

Mikhail G. Voronkov and Klavdiya A. Abzaeva

F. Compounds Containing an Sn O Bond . . . . . . . . . . . . . . . . . .
G. Compounds Containing an Sn E Bond (E D S, Se, N, P) . . . . . .
H. Compounds Containing Sn Sn or Sn M Bond . . . . . . . . . . . . .
I. Compounds of Nontetracoordinated Tin . . . . . . . . . . . . . . . . . .
J. Biological Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
K. Practical Use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
IV. ORGANOLEAD COMPOUNDS . . . . . . . . . . . . . . . . . . . . . . . . .
A. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
B. Synthesis from Metallic Lead and its Alloys . . . . . . . . . . . . . . .
C. Metallorganic Approaches to Organolead Compounds . . . . . . . . .
D. Nonorganometallic Approaches to the Formation of a C Pb Bond
E. Cleavage of the C Pb and Pb Pb Bond . . . . . . . . . . . . . . . . .
F. Compounds having a Pb O Bond . . . . . . . . . . . . . . . . . . . . . .

G. Compounds having a Pb S, Pb Se and Pb Te Bond . . . . . . . .
H. Compounds having a Pb N Bond . . . . . . . . . . . . . . . . . . . . . .
I. Organolead Hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
J. Compounds Containing a Pb Pb Bond . . . . . . . . . . . . . . . . . .
K. Biological Activity and Application of Organolead Compounds . .
V. CONCLUSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
VI. REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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98

I. INTRODUCTION

Germanium, tin and lead are members of one family, called the silicon subgroup. Sometimes these elements are called mesoids as well, due both to their central position in the
short version of Mendeleev’s Periodic Table and to their valence shells, which occupy an
intermediate place among the I–VII Group elements1 . They can also be called the heavy
elements of Group 14 of the Periodic Table.
The history of the silicon prototype of this family and its organic derivatives is elucidated in detail in the literature2 – 5 . In contrast, we could not find any special accounts
dealing with the history of organic germanium, tin and lead compounds. The only exception is a very brief sketch on the early history of the chemistry of organotin compounds6 .
Some scattered information on the organic compounds of germanium, tin and lead can be
found in some monographs and surveys. In this chapter we try to fill the gaps in this field.
Humanity first encountered the heavy elements of Group 14 at different times; with
germanium, it happened quite unusually in the middle of the 19th century. As with
the discovery of the planet Neptune7 , which was first predicted by astronomers and
almost immediately discovered, Mendeleev, who predicted the existence of three hitherto
unknown elements, reported at the Russian Chemical Society session on December 10,
1870 on the discovery of one of these elements as follows: ‘. . .to my mind, the most interesting among undoubtedly missing metals will be one that belongs to Group IV and the
third row of the Periodic Table, an analog of carbon. It will be a metal, following silicon,
so we call it ‘eca-silicon’8 . Moreover, Mendeleev even predicted the physical and chemical properties of the virtual element9 – 12 . Having no conclusive proof of the existence
of eca-silicon, Mendeleev himself began experimental investigations aimed at finding it
in different minerals13 . It is noteworthy that as early as 1864 Newlands14 and Meyer15
suggested the possible existence of an element like eca-silicon and predicted its atomic
weight. However, Mendeleev was the first to predict properties of the element in detail.
Fifteen years later the German chemist Winkler16,17 , working at the Freiberg Academy
of Mines, was able to isolate during the investigation of a recently discovered mineral argirodit (Ag6 GeS5 ) a new element in its free state. Initially, Winkler wanted to


1. Genesis and evolution in the organic chemistry of Ge, Sn, and Pb compounds


3

name the new element neptunium, after the newly discovered planet Neptune. However,
this name seemed to be given for another falsely discovered element, so he called the
new element germanium in honor of his motherland18 – 21 . At the time several scientists sharply objected to this name. For example, one of them indicated that the name
sounded like that of the flower Geranium while another proposed for fun to call the
new element Angularium, i.e. angular (causing debates). Nevertheless, in a letter to Winkler, Mendeleev encouraged the use of the name germanium. It took same time until
the identity of eca-silicon and germanium was established18 – 22 . Polemics, as to which
element germanium is analogous flared up ardently. At first, Winkler thought that the
newly discovered element filled the gap between antimony and bismuth. Having learned
about Winkler’s discovery, almost simultaneously in 1886 Richter (on February 25, 1886)
and Meyer (on February 27, 1886) wrote him that the discovered element appeared to
be eca-silicon. Mendeleev first suggested that germanium is eca-cadmium, the analog of
cadmium. He was surprised by the origin of the new element, since he thought that ecasilicon would be found in titanium–zirconium ores. However, very soon, he rejected his
own suggestion and on March 2, 1886, he wired Winkler about the identity of germanium
and eca-silicon. Apparently, this information raised doubts in Winkler’s mind about the
position of germanium in the Periodic Table. In his reply to Mendeleev’s congratulation
he wrote: ‘. . .at first I was of the opinion that the element had to fill up the gap between
antimony and bismuth and coincide with eca-stibium in accordance with your wonderful,
perfectly developed Periodic Table. Nevertheless, everything showed us we dealt with
a perfectly well developed Periodic Table. But everything implied that we are dealing
with eca-silicon23 . The letter was read at the Russian Physical and Chemical Society
section on March 7. Winkler reported that the properties of the element and its common
derivatives corresponded closely to those predicted for eca-silicon. A second letter by
Winkler was read in a Chemical Section meeting of the Russian Physical and Chemical Society on May 1,1886. Winkler reported that the properties of germanium and its
simpler derivatives were surprisingly very similar to those predicted for eca-silicon22,24 .
This is reported in Winkler’s paper in the Journal of the Russian Physical and Chemical Society entitled ‘New metalloid Germanium’, translated into Russian at the author’s
request25,26 .
An inspection of Table 1 impresses one by the precise way in which Mendeleev predicted the properties of germanium and its elementary derivatives.
In 1966, Rochow27 somewhat criticized the accuracy of Mendeleev’s predictions of the

properties of eca-silicon (germanium). He stated: ‘Mendeleev predicted that eca-silicon
would decompose steam with difficulty, whereas germanium does not decompose it at
TABLE 1. The properties of eca-silicon (Es) and its
derivatives predicted by Mendeleev9 – 12,19,20 in comparison with the properties of germanium and several
germanium derivatives24 – 30
Properties

M D Es

M D Ge

Atomic weight
Specific weight
Atomic volume
Specific weight of MO2
B.p. of MCl4
Specific weight of MCl4
B.p. of M(C2 H5 )4
Specific weight of M(C2 H5 )4

72.0
5.5
13.0
4.7
ca 90°
1.9
ca 160°
0.96

72.3

5.469
13.2
4.703
88°
1.887
160°
1.0


4

Mikhail G. Voronkov and Klavdiya A. Abzaeva

all. This is to say that germanium is less metallic than was predicted. Mendeleev also
said that acids would have a slight action on the element, but they have none; again it
is a more negative element than was predicted. There are many more chemical facts31
which point in the same direction: germanium is more electronegative than was expected
by interpolation, and it actually behaves a great deal like arsenic’. Rochow was right to
some extent. It is known32,33 that in accordance with Mendeleev’s predictions germanium
has more metallic characteristics than silicon; in a thin layer or under high temperatures
germanium reacts with steam, and it reacts very slowly with concentrated H2 SO4 , HNO3 ,
HF and Aqua Regia. In relation to the Allred and Rochow electronegativity scale34,35 the
electronegativity of germanium is higher than that of silicon. However, according to other
scales36 – 39 and to Chapter 2 of this book, the electronegativity of germanium is lower or
approximately the same as that for silicon. As illustrated in Table 1 Mendeleev predicted
not only the possibility of existence, but also the properties of the simple organogermanium
derivative Et4 Ge.
It is noteworthy that Winkler synthesized Et4 Ge in 188723,29 . Its properties were consistent with those predicted by Mendeleev. Organogermanium chemistry was born at
this time.
In contrast to germanium the exposure of mankind to tin and lead was much earlier and

not so dramatic18 – 21,28 . These two elements belong to the seven main elements known
to ancient man40 . Up to the seventeenth century, tin and lead were often confused, as
is witnessed by their Latin names, i.e. Plumbum album, Plumbum candidum (Sn) and
Plumbum nigrum (Pb). Tin was known in countries of the Near East at least from the
middle of the third millennium BC. Lead became known to the Egyptians at the same
time as iron and silver, and very probably earlier than tin19,28 .
Many of Mendeleev’s predecessors (Pettenkofer, Dumas, Cooke, Graham and others)
assumed that tin and lead cannot belong to the same group as silicon12 and Mendeleev
was the first to include them in the same group of his Periodic Table with silicon and ecasilicon. He made this courageous prediction based on the assumption that the unknown
element eca-silicon should have properties intermediate between metals and nonmetals
and that all these elements, including carbon, should belong to one group.
The forefather of the chemistry of organic compounds of tin and lead was the Swiss
chemist Carl Lăowig. In the middle of the nineteenth century in the Zurich University
laboratory (which was not set up to handle toxic compounds), he developed for the
first time several methods for the synthesis of common organic derivatives of these two
elements and described their properties41 – 44 .
Following Edward Frankland, who paid attention to organotin compounds as early as
185345 , Lăowig became one of the founders of organometallic chemistry but, unfortunately,
historians of chemistry have forgotten this. In spite of his work with rather toxic organotin
and organolead compounds during a period of several years in the absence of safety
precautions, Lăowig lived a long life and died only in 1890 due to an accident.
It is necessary to outline the nomenclature that we use before starting to develop the genesis and evolution of the chemistry of organic derivatives of heavy elements of Group 14.
From the moment of their appearance and to some extent up to now, the names of organic
derivatives of tin and lead were based on the name of the corresponding metals. It should
be mentioned that tin and lead are called quite differently in English, German, French
and Russian — Tin, Zinn, Etein, oLOWO, and Lead, Blei, Plomb, sWINEC, respectively. In
addition, archaic names of these compounds (such as trimethyltin oxide and alkylgermanium acid) are incompatible with the modern nomenclature of organosilicon compounds,
which are the prototypes of this mesoid group. In this chapter we use the nomenclature
of organic compounds of germanium, tin and lead approved by IUPAC46 in analogy with
the nomenclature of organosilicon compounds, based on their Latin names (Germanium,



1. Genesis and evolution in the organic chemistry of Ge, Sn, and Pb compounds

5

Stannum, Plumbum). It is not the central metallic atom that is named, but only its hydride
MH4 (germane, stannane, plumbane) and the substituents which replace hydrogen atoms
in the hydride molecule. Compounds in which the metal atom valence is either higher or
lower than 4 are named in analogy to the nomenclature of organosilicon compounds.
In this chapter, we have tried to gain some insight into the genesis and development
of the chemistry of organic germanium, tin and lead compounds up to the end of the
20th century. We have also paid attention to the work of the early researchers which
was sometimes forgotten in spite of their tedious work under more difficult conditions
than in the present time, which laid the fundamental laws of the chemistry of organic
germanium tin and lead compounds. The organic chemistry of the heavy elements (Ge, Sn,
Pb) of the silicon sub-group has been previously reviewed extensively either in reviews
devoted to organic derivatives of all these elements1,47 – 73 or in separate reviews on
organogermanium74 – 86 , organotin87 – 106 and organolead compounds107 – 112 .
Valuable information can be also found in chapters devoted to organometallic
compounds113 – 123 and in many surveys124 – 138 . Excellent bibliographical information on
reviews devoted to organogermanium (369 references)79 , organotin (709 references)100
and organolead compounds (380 references)112 have been published in Russia.
Unfortunately, all the literature cited did not review the historical aspect, so our attempt
to extract from that vast body of information the chronological order of the genesis and
development of the organic chemistry of germanium tin, and lead compounds was not
an easy task. It forces us to re-study numerous original publications, in particular those
published in the 19th century. Nevertheless, the references presented in chronological
order still do not shed light on the evolution of this chemistry, but they have important
bibliographic value.

II. ORGANOGERMANIUM COMPOUNDS
A. Re-flowering after Half a Century of Oblivion

Up to the middle of the 20th century organogermanium derivatives were the least understood among the analogous compounds of the silicon subgroup elements. As mentioned
above23,29 the first organogermanium compound, i.e. tetraethylgermane, was synthesized for the first time by Winkler in 1887 by the reaction of tetrachlorogermane and
diethylzinc23,29 , i.e. a quarter century later than the first organic compounds of silicon,
tin and lead were obtained.
The synthesis of Et4 Ge proved unequivocally that the germanium discovered by Winkler
belong to Group IV of the Periodic Table and that it was identical to Mendeleev’s ecasilicon. Consequently, Winkler was the forefather of both the new germanium element and
also the chemistry of its organic derivatives, whereas Mendeleev was their Nostradamus.
During the period between 1887 and 1925 no new organogermanium compound was
reported. The forty years of the dry season resulted mainly from the scarcity and high
prices of germanium and its simplest inorganic derivatives. This reflected the low natural reserves of argirodit, the only mineral source of germanium known at that time.
The picture changed dramatically when in 1922 new sources of germanium were discovered. In particular, 0.1–0.2% of Ge were found in a residue of American zinc ore
after zinc removal139,140 . Dennis developed a method for the isolation of tetrachlorogermane from the ore141 . In 1924, 5.1% of Ge was found in germanite, a mineral from
southwestern Africa. Rhenierite, a mineral from the Belgian Congo, containing 6–8%
of Ge142 , became another source of germanium. In 1930–1940, processing wastes of
coal ashes and sulfide ores became the main sources of germanium34,141,143,144 . These
developments allowed American, English and German chemists to start in 1925 to carry


6

Mikhail G. Voronkov and Klavdiya A. Abzaeva

out fundamental investigations of organogermanium compounds, in spite of the fact that
germanium was still very expensive145 – 150 .
Thus, the chemistry of organogermanium compounds actually started to develop
in the second quarter of the twentieth century. Its founders were L. M. Dennis,
C. A. Kraus, R. Schwartz and H. Bayer, whose results were published in 1925–1936.

A period of low activity then followed in this field and was resumed only in the
middle of the century by leaders such as E. Rochow, H. Gilman, H. H. Anderson,
O. H. Johnson, R. West and D. Seyferth. Organogermanium chemistry started to
flourish in the sixties when many new investigators joined the field. These included
the French chemists M. Lesbre, J. Satge and P. Mazerolles, the German chemists
M. Schmidt, H. Schmidbaur, M. Wieber, H. Schumann and J. Ruidisch, the English
chemists F. Glockling and C. Eaborn, the Russian chemists V. F. Mironov, T. K. Gar,
A. D. Petrov, V. A. Ponomarenko, O. M. Nefedov, S. P. Kolesnikov, G. A. Razuvaev,
M. G. Voronkov and N. S. Vyazankin, the Dutch chemist F. Rijkens the American chemist
J. S. Thayer and others.
Activity was stimulated by the intensive development of the chemistry of organometallic
compounds, particularly of the silicon and tin derivatives. The chemistry of organogermanes was significantly developed as well due to the essential role of germanium itself
and its organic derivatives in electronics151,152 , together with the discovery of their biological activities (including anticancer, hypotensive, immunomodulating and other kinds
of physiological action)80,81,86,153 . In addition, a progressive decrease in the prices of elemental germanium and its derivatives expanded their production and helped their growth.
The rapid expansion of organogermanium chemistry is clearly evident due to the increase
in the number of publications in this field.
From 1888 till 1924 there were no publications and prior to 1934 just 26 publications were devoted to organogermanes154 . Only 25 references on organogermanium
compounds were listed in an excellent monograph by Krause and Grosse published in
1937155 ; 60 publications appeared before 1947156 , 99 before 1950157 and 237 during the
period 1950–196048,78 By 1967 the number of publications was over 1800 and by 1971
it exceeded 300036,37 . By 1970 about 100 publications had appeared annually36,79 and
by this time 370 reviews dealing with organogermanium compounds had appeared79 .
In 1951 already 230 organogermanium compounds were known157 , in 1961 there were
260158 and in 1963 there were more than 700159 .
As the chemistry of organogermanium compounds is three-quarters of a century younger
than the organic chemistry of tin and lead, it is reasonable to consider in this chapter the
most important references published before 1967, when two classical monographs were
published36,37,78 . Due to space limitation we will avoid, where possible, citing reaction
equations in the hope that they will be clear to the readers.
B. Organometallic Approaches to a C−Ge and Ge−Ge Bond


Thirty-eight years after Winkler developed the organozinc method for the synthesis of
tetraethylgermane, Dennis and Hance160 reproduced it, but this method for synthesis of
aliphatic germanium derivative was not used later. However, in the years 1927–1935
arylzinc halides were used for the synthesis of tetraarylgermanes23,161 – 165 .
Application of Grignard reagents in organometallic synthesis led to the synthesis
of common aliphatic, aromatic and alicyclic germanium derivatives during the years
1925–1932. Dennis and Hance160 were the first to produce in 1925 tetraalkylgermanes
R4 Ge (R D Me, Et, Pr, Bu, Am)145,160,166 – 169 from Grignard reagents. Kraus and
Flood148 used organomagnesium reagents for the synthesis of tetraalkylgermanes. In 1925
Morgan and Drew149 , and later Kraus and Foster161 synthesized tetraphenylgermane, the


1. Genesis and evolution in the organic chemistry of Ge, Sn, and Pb compounds

7

first compound having a Ph Ge bond, from GeCl4 and PhMgBr. The maximum (70–75%)
yield was reached at a GeCl4 : PhMgBr ratio of 1 : 5170,171 .
In 1934 Bauer and Burschkies172 , and only later other researchers173 – 176 showed for
the first time that a reaction of GeCl4 and Grignard reagents results in hexaorganyldigermanes R3 GeGeR3 (R D 4-MeC6 H4 and PhCH2 ). In 1950, Johnson and Harris173 noted the
formation of hexaphenyldigermane in the reaction of GeCl4 with an excess of PhMgBr.
Glocking and Hooton177,178 later found that if the above reaction was carried out in
the presence of magnesium metal, hexaphenyldigermane Ph3 GeGePh3 was produced in a
higher yield along with Ph4 Ge. Seyferth176 and Glockling and Hooton178 concluded that
the intermediate product in the reaction of GeGl4 and ArMgBr leading to Ar3 GeGeAr3
was Ar3 GeMgBr.
In line with this assumption Gilman and Zeuech179 found in 1961 that Ph3 GeH
reacted with several Grignard reagents (such as CH2 DCHCH2 MgX or ArMgBr) to give
Ph3 GeMgX (X D Cl, Br). The latter has cleaved THF, since a product of the reaction

followed by hydrolysis seemed to be Ph3 Ge(CH2 )4 OH. Mendelsohn and coworkers180
indicated the possibility of the formation of R3 GeMgX in the reaction of GeCl4 and
Grignard reagents.
In the period 1931–1950 the organomagnesium syntheses became the laboratory practice for preparing tetraorganylgermanes.
Tetraalkyl- and tetraarylgermanes containing bulky organic substituents could be synthesized only with difficulty, if at all, using Grignard reagents. In this case the reaction
resulted in triorganylhalogermane181 – 183 .
Organylhalogermanes R4 n GeXn (n D 1–3) were prepared for the first time in 1925
by Morgan and Drew149 , who isolated phenylbromogermanes Ph4 n GeBrn (n D 1, 3)
together with tetraphenylgermane from the reaction of GeBr4 and PhMgBr. However, the
organomagnesium synthesis of organylhalogermanes has not found much use due to the
simultaneous production of other compounds and the difficulty of separating them. The
only exceptions were R3 GeX products having bulky R substituents172,181,183,184 .
In the reaction of HGeCl3 and MeMgBr, Nefedov and Kolesnikov185 obtained a mixture
of both liquid and solid permethyloligogermanes Me(Me2 Ge)n Me.
In 1932, Krause and Renwanz186 synthesized the first heterocyclic organogermanium
compound, tetra-2-thienylgermane, from the corresponding Grignard reagent. In the same
year Schwarz and Reinhardt150 synthesized by the same method the first germacycloalkanes (1,1-dichloro- and 1,1-diethyl-1-germacyclohexanes). They also synthesized tetra-Npyrrolylgermane by the reaction of GeCl4 and potassium pyrrole.
Since 1926 the organomagnesium synthesis was also used for preparing more complex
tetraorganylgermanes145,162,163,169,172,187 – 190 such as R3 GeR0 , R2 GeR02 and R2 GeR0 R00 .
The first unsaturated organogermanium compounds having α,β- or β,γ -alkynyl groups
at the Ge atom were synthesized in 1956–1957 by Petrov, Mironov and Dolgy191,192 and
by Seyferth176,193,194 using Grignard or Norman reagents.
In 1925, the Dennis group used along with the organozinc and organomagnesium
synthesis of tetraorganylgermanes, also the Wurtz–Fittig reaction (i.e. the reaction of
aryl halides with sodium metal and tetrahalogermanes168,187,195 ). The Wurtz–Fittig reaction was extensively employed for the synthesis of organogermanium compounds having Ge Ge bonds such as R3 GeGeR3 . The first representative of the Ph3 GeGePh3
series was synthesized in 1925 by Morgan and Drew149 , and subsequently by Kraus
and coworkers161,196 , using the reaction of triphenylbromogermane and sodium metal
in boiling xylene. Analogously, Bauer and Burschkies172 produced in 1934 R3 GeGeR3 ,
R D 4-MeC6 H4 and PhCH2 . In addition, they found that the reaction of GeCl4 , Na and
RBr (R D 4-MeC6 H4 ) led to R3 GeGeR3 in good yield together with R4 Ge. In 1932,



8

Mikhail G. Voronkov and Klavdiya A. Abzaeva

Kraus and Flood148 found that hexaethyldigermane was not formed in the reaction of
triethylbromogermane and sodium metal in boiling xylene. However, they produced hexaethyldigermane by heating Et3 GeBr and Na in a sealed tube at 210–270 ° C without solvent
or by the reaction of Et3 GeBr and Na in liquid ammonia.
The possibility of producing diphenylgermylene alkali metal derivatives like Ph2 GeM2
(M D Li, Na) was shown in 1952 by Smyth and Kraus197 when they obtained Ph2 GeNa2
by cleavage of Ph4 Ge with concentrated solution of sodium in liquid ammonia. In 1930,
Kraus and Brown198 produced a mixture of perphenyloligocyclogermanes (Ph2 Ge)n by
the reaction of sodium metal with diphenyldichlorogermane in boiling xylene. However,
only in 1963 did Neumann and Kăuhlein199 show that the main crystalline product of the
reaction is octaphenylcyclotetragermane (Ph2 Ge)4 . Cleavage of (Ph2 Ge)n with sodium in
liquid ammonia resulted in Ph2 GeNa2 . Reaction of (PhGe)4 with iodine which resulted
in cleavage of the Ge Ge bond, allowed the authors199 to synthesize the first organotetragermanes involving three Ge Ge bonds X[Ph2 Ge]4 X (X D I, Me, Ph). By the reaction of diphenyldichlorogermane and lithium (or sodium naphthalene) Neumann and
Kuhlein175,199,200 isolated higher perphenylcyclogermanes with n D 5 (37%) and n D 6
(17%). It is particularly remarkable that, unlike their homologs with n D 4, these compounds could not be cleaved with iodine.
In 1962–1965 Nefedov, Kolesnikov and coworkers201 – 205 investigated the reaction of
Me2 GeCl2 with lithium metal in THF. The main products were (Me2 Ge)6 (80% yield) at
20–45 ° C and the polymer (Me2 Ge)n (50% yield) at 0 ° C.
In 1966 Shorygin, Nefedov, Kolesnikov and coworkers206 were the first to investigate
and interpret the UV spectra of permethyloligogermanes Me(Me2 Ge)n Me(n D 1–5). The
reaction of Et2 GeCl2 with Li in THF led mostly to polydiethylgermane (Et2 Ge)n 207 . At
the same time Mironov and coworkers208,209 obtained dodecamethylcyclohexagermane
(Me2 Ge)6 by the same procedure.
In 1969, Bulten and Noltes210 synthesized the perethyloligogermanes Et(Et2 Ge)n Et
(n D 2–6) by the organolithium method. The oligomer with n D 6 was thermally stable

and heating at 250 ° C for 8 hours resulted in only 20% decomposition.
By a reaction of Li amalgam with Ph2 GeBr2 , Metlesics and Zeiss211 produced 1,2dibromotetraphenyldigermane instead of the cyclic oligomers obtained previously in a similar reaction with Li metal. A reaction of Li amalgam with PhGeBr3 gave PhBr2 GeGeBr2 Ph,
the thermolysis of which resulted in PhGeBr3 .
Curiously, the reaction of phenyltrichlorogermane with sodium or potassium produced
a compound (PhGe)n , which Schwarz and Lewinsohn187 mistook for hexaphenylhexagermabenzene Ph6 Ge6 . Five years later Schwartz and Schmeisser212 found that the action
of potassium metal on PhGeCl3 yielded a product, assigned by them to be a linear hexamer having terminal Ge(III) atoms i.e. a biradical of a structure ž (PhGeDGePh)ž . They
thought that this structure could be confirmed by addition reactions with bromine, iodine
and oxygen, which indeed took place. However, HI and HBr were not involved in the
addition reactions.
Two dozen years later Metlesics and Zeiss213 obtained the same product by the reaction
of PhGeCl3 with Li amalgam. They found that the product was a polymer consisting of
(PhGe)n , (Ph2 Ge)n and (PhGeO)n chains.
In 1950–1960 it was found that triarylgermyl derivatives of alkali metals could
be obtained by cleavage of Ge H214,215 , C Ge174,195,216,217 , Ge Ge218 – 221 and
Ge Hal222 bonds by Li, Na or K in the appropriate solvents.
In 1950, Glarum and Kraus214 investigated the reaction of alkylgermanes R4 n GeHn
(n D 1–3) and sodium metal in liquid ammonia. They found that alkylgermanes RGeH3
reacted with Na to give RGeH2 Na.