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Organogermanium Compounds.
Theory, Experiment, and Applications

Vladimir Ya. Lee
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Organogermanium Compounds
Organogermanium Compounds
Theory, Experiment, and Applications
Edited by Vladimir Ya. Lee
Volume 1
This edition first published 2023
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v
Full Table of Contents
Volume 1:
Preface ix
List of Contributors xiii
1 Computational and Theoretical Aspects of Structure and Bonding in Doubly Bonded Organogermanium
Compounds 1
Miriam Karni and Yitzhak Apeloig
2 Organogermanium Compounds of the Main Group Elements 103

Kirill V. Zaitsev
3 Transition Metal Complexes of Germanium 195

Kohtaro Osakada
4 Germanium Cages and Clusters 225

Tanja Kunz and Andreas Schnepf
5 Arylgermanium Hydrides, ArnGeH4-n (n = 1–3) - Synthesis, Characterization, Reactivity 277

Ana Torvisco and Frank Uhlig
6 Germylium Ions and Germylium Ion-like Species 299

Thomas Müller
7 Germanium-Containing Radicals 339

Alexander Hinz and Frank Breher
8 Germanium-Centered Anions 361

Christoph Marschner
9 Germylenes 387
Norio Nakata
10 Multiple Bonds to Germanium 435

Vladimir Ya. Lee
vi Full Table of Contents
Volume 2:
Preface vii
List of Contributors xi
11 Germaaromatic Compounds 477

Yoshiyuki Mizuhata and Norihiro Tokitoh
12 Germanium-centered Ion Radicals 507

Mikhail P. Egorov, Viatcheslav V. Jouikov, Elena N. Nikolaevskaya, and Mikhail A. Syroeshkin
13 Donor-acceptor Stabilization of Species with Low-coordinate Germanium 561

Sakya S. Sen and Herbert W. Roesky
14 Synthesis of the Penta- and Hexacoordinate Germanium(IV) Complexes 597

Naokazu Kano
15 Dynamic Stereochemistry of Penta- and Hexacoordinate Germanium(IV) Complexes 629

Vadim V. Negrebetsky and Alexander A. Korlyukov
16 X-ray Crystallography of Organogermanium Compounds 667

Catherine Hemmert and Heinz Gornitzka
17 Organogermanium Photochemistry 745

William J. Leigh
18 Oligo- and Polygermanes 787

Charles S. Weinert
19 Bioorganic and Medicinal Organogermanium Chemistry 839

Takashi Nakamura, Yasuhiro Shimada, and Katsuyuki Sato
Index 867
vii
Contents
Preface ix
List of Contributors xiii
1 Computational and Theoretical Aspects of Structure and Bonding in Doubly Bonded Organogermanium
Compounds 1
2 Organogermanium Compounds of the Main Group Elements 103

Kirill V. Zaitsev
3 Transition Metal Complexes of Germanium 195

Kohtaro Osakada
4 Germanium Cages and Clusters 225

Tanja Kunz and Andreas Schnepf
5 Arylgermanium Hydrides, ArnGeH4-n (n = 1–3) - Synthesis, Characterization, Reactivity 277

Ana Torvisco and Frank Uhlig
6 Germylium Ions and Germylium Ion-like Species 299

Thomas Müller
7 Germanium-Containing Radicals 339

Alexander Hinz and Frank Breher
8 Germanium-Centered Anions 361

Christoph Marschner
9 Germylenes 387
Norio Nakata
10 Multiple Bonds to Germanium 435

Vladimir Ya. Lee
ix
Preface
Germanium is one of the few chemical elements in the Periodic Table, for which the theoret-
ical prediction of its very existence has preceded its actual experimental discovery. This predic-
tion was made by the Russian chemist Dmitri Mendeleev based on the general trends of valence
and atomic weights within his Periodic Table of the chemical elements (1869) [D. Mendelejeff
“Ueber die Beziehungen der Eigenschaften zu den Atomgewichten der Elemente”, Z. Chem.
1869, 12, 405–406]. In an updated version of this Periodic Table (1871-1872) [D. Mendelejeff
“Die Periodische Gesetzmässigkeit der Chemischen Elemente”, Ann. Chem. Pharm. 1872,
Suppl. 8, 133–229; D. Mendelejeff “Zur Frage über das System der Elemente”, Ber. Dtsch. Chem.
Ges. 1871, 4, 348–352], Mendeleev proposed that there was a missing element in the carbon
family with the atomic weight 72 that should be placed in the fourth row, just below silicon and
just above tin within the carbon group. He named this non-existing (at that time) element as
“eka-silicium”. Following this seminal Mendeleev prediction, German chemist Clemens
Winkler finally succeeded in 1886 in the isolation of “eka-silicium” from the mineral argyrodite (Ag8GeS6) and named this
new element as germanium (Ge) [C. Winkler “Germanium, Ge, Ein Neues, Nichtmetallisches Element”, Ber. Dtsch. Chem.
Ges. 1886, 19, 210–211; C. Winkler “Mittheilungen über das Germanium”, J. Prakt. Chem. 1886, 34, 177–229]. Winkler also
pioneered the preparation of the first organic derivative of germanium, namely, tetraethylgermane Et4Ge, in 1887 [C.
Winkler “Mittheilungen über das Germanium”, J. Prakt. Chem. 1887, 36, 177–209]. Since then and up the present date, the
chemistry of organogermanium compounds (that is, compounds featuring Ge–C bonds) has experienced an explosive
growth, especially after the recognition of the key role of metallic germanium in semiconductor electronics in the mid-
twentieth century, followed by the extensive use of germanium and its organic derivatives in optical fibers, polymerization
catalysts, microchip manufacturing, and biomedical applications. Given the undoubted importance of organogermanium
compounds, it comes as no surprise that the field of organogermanium chemistry is continuously growing, thus requiring
regular reviewing and updates on its latest advances. Among the most important previously published books on organo-
germanium chemistry, one should first of all mention excellent monograph by Satgé and coworkers [J. Satgé, M. Lesbre, P.
Mazerolles, “The Organic Compounds of Germanium, Wiley, 1971] and two comprehensive volumes of the Patai’s series of
books [(a) The Chemistry of Organic Germanium, Tin, and Lead Compounds (Eds. S. Patai, Z. Rappoport), Wiley, 1995; (b)
The Chemistry of Organic Germanium, Tin, and Lead Compounds, Volume 2 (Ed. Z. Rappoport), Volume 2, Parts 1–2, Wiley,
2002]. Patai’s latest book was published 20 years ago, and since then, critical progress has been made in organogermanium
chemistry with the majority of milestone developments achieved since 2000. That is why we have attempted in this book
to survey, analyze and summarize the current state of affairs in the field of organogermanium chemistry, focusing on the
latest (published mostly after 2000) groundbreaking advances with comprehensive and up-to-date literature coverage up
to the end of 2021.
Our “Organogermanium Compounds” book is organized into the three major parts, Theory, Experiment, and
Applications, made up of a total of 19 chapters, each written by leading experts in their respective fields comprehensively
covering the relevant literature, first published within the last two decades.
1) The first part, Theory (one chapter) includes a contribution “Computational Aspects of Structure and Bonding in
Doubly Bonded Organogermanium Compounds” from Miri Karni and Yitzhak Apeloig (Technion – Israel Institute of
Technology, Haifa, Israel). In their chapter, the authors present state-of-the-art computational approaches to the flourish-
ing field of doubly bonded organogermanium compounds and thoroughly discuss their structural and bonding aspects
depending on the nature of the double bond and its substituents.
x Preface
2) The second part, Experiment (16 chapters), deals with the most fundamental experimental advances that were
achieved in synthetic and physico-chemical studies, and is accordingly divided into two sections, Synthesis of
Organogermanium Compounds and Physico-Chemical Studies of Organogermanium Compounds. The first section, Synthesis
of Organogermanium Compounds, is further subdivided into three subsections (in accord with the coordination number of
the central germanium): 1) Organogermanium Compounds of Tetracoordinate Germanium, 2) Organogermanium
Compounds of Low-Coordinate Germanium, 3) Organogermanium Compounds of Hypercoordinate Germanium.
In the first subsection, Organogermanium Compounds of Tetracoordinate Germanium, there are four contributions. Kirill
V. Zaitsev (Moscow State University, Moscow, Russia) in his chapter “Organogermanium Compounds of the Main Group
Elements” provides a detailed overview of synthetic and structural aspects of organogermanium compounds containing
Ge–E bonds (where E is an element of groups 13–17). The following chapter “Transition Metal Complexes of Germanium”
by Kohtaro Osakada (Tokyo Institute of Technology, Tokyo, Japan) comprehensively covers chemistry of transition metal
complexes featuring metal–germanium single bonds. In their chapter “Germanium Cages and Clusters”, Tanja Kunz and
Andreas Schnepf (University of Tübingen, Tübingen, Germany) discuss syntheses, structural characterization, and reac-
tivity of germanium clusters of the polyhedral-, metalloid-, and Zintl-type. In the final chapter of this subsection,
“Arylgermanium Hydrides RnGeH4–n (n = 1–3) – Synthesis, Characterization, Reactivity”, Ana Torvisco and Frank Uhlig
(Graz University of Technology, Graz, Austria) describe a variety of aryl-substituted organogermanium hydrides focusing
on their synthesis, structural aspects (including 73Ge NMR properties), and selected applications.
The most abundant second subsection (eight chapters), Organogermanium Compounds of Low-Coordinate Germanium,
focuses on the emerging field concerned with the stable germanium analogues of pivotal organic reactive intermediates,
such as germanium-centered cations, free radicals, anions, ion-radicals, germylenes, multiply-bonded organogermanium
compounds, germaaromatics, and donor-acceptor complexes of low-coordinate germanium. In the first chapter in this sub-
section, “Germylium Ions and Germylium Ion-Like Species”, Thomas Müller (University of Oldenburg, Oldenburg,
Germany) summarizes the chemistry of germylium ions [R3Ge]+ and ion-like species [R3Ge(Do)]+ (Do = electron donor)
with particular emphasis on their synthesis, characterization, and specific reactivity. The chapter “Germanium-Containing
Radicals” by Alexander Hinz and Frank Breher (Karlsruhe Institute of Technology, Karlsruhe, Germany) discusses general
methods for generation and isolation of Ge-centered radicals (including those with redox-non-innocent ligands), polyradi-
cals, as well as their reactivity and synthetic applications. The following chapter “Germanium-Centered Anions”, written
by Christoph Marschner (Graz University of Technology, Graz, Austria), focuses on the general methods for the prepara-
tion and synthetic utilization of a variety of germyl anions, as well as germyl dianions, and compounds with a negative
charge on the sp2 Ge atom. Recent advances in the field of the stable germylenes (including N-heterocyclic germylenes)
and their transition metal complexes, with focus on their preparation, characterization and specific reactivity, are pre-
sented in the chapter “Germylenes” by Norio Nakata (Saitama University, Saitama, Japan). The story of the low-coordinate
organogermanium compounds is further continued by Vladimir Ya. Lee (University of Tsukuba, Tsukuba, Japan) in his
chapter “Multiple Bonds to Germanium,” which summarizes the latest developments in the field of doubly and triply
bonded organogermanium derivatives containing both homonuclear and heteronuclear multiple bonds. Another challeng-
ing topic of contemporary organogermanium chemistry, namely, germaaromatic compounds (both neutral and charged)
including non-classical aromatic systems, is overviewed by Yoshiyuki Mizuhata and Norihiro Tokitoh (Kyoto University,
Kyoto, Japan) in their chapter “Germaaromatic Compounds”. The following chapter “Germanium-Centered Ion Radicals”,
written by Mikhail P. Egorov, Viatcheslav V. Jouikov, Elena N. Nikolaevskaya, and Mikhail A. Syroeshkin (Institute of
Organic Chemistry, Moscow, Russia and University of Rennes, Rennes, France), covers recent progress in the field of
anion-radicals and cation-radicals discussing general methods for their generation and identification, both experimental
and computational. The Organogermanium Compounds of Low-Coordinate Germanium subsection is completed by a con-
tribution “Donor-Acceptor Stabilization of Species with Low-Coordinate Germanium” by Sakuya S. Sen and Herbert W.
Roesky (National Chemical Laboratory, Pune, India and University of Göttingen, Göttingen, Germany), which highlights
the progress in the field of compounds with low-coordinate germanium stabilized by donor-acceptor interactions.
The Synthesis of Organogermanium Compounds section ends with the subsection Organogermanium Compounds of
Hypercoordinate Germanium containing two contributions. In the first one, “Synthesis of the Penta- and Hexacoordinate
Germanium(IV) Complexes”, Naokazu Kano (Gakushuin University, Tokyo, Japan) classifies the title compounds bearing
bi-, tri-, and tetradentate ligands (as well as carbene ligands), and discusses their synthesis and reactivity. The second con-
tribution “Dynamic Stereochemistry of Penta- and Hexacoordinate Germanium(IV) Complexes”, written by Vadim V.
Negrebetsky and Alexander A. Korlyukov (Russian National Research Medical University, Moscow, Russia and Institute
of Organoelement Compounds, Moscow, Russia), summarizes and analyzes the data on stereochemical processes involving
organic complexes of hypercoordinate germanium.
Preface xi
The Experiment part is completed by the Physico-Chemical Studies of Organogermanium Compounds section which
comprises two contributions each dealing with state-of-the-art instrumental techniques for assessing the structures of
organogermanium compounds. In the first one, “X-Ray Crystallography of Organogermanium Compounds”, Catherine
Hemmert and Heinz Gornitzka (University of Toulouse, Toulouse, France) comprehensively overview the vast literature
on the structurally characterized organogermanium compounds discussing their particular X-ray crystallographic fea-
tures. The following chapter “Organogermanium Photochemistry”, by William J. Leigh (McMaster University, Hamilton,
Canada) deals with developments in the photochemistry of organogermanium compounds, particularly emphasizing sys-
tems involving low-coordinate organogermanium compounds as either photoproducts or photoreactants.
3) The last, third, part of the book, Applications (two chapters), reports on the synthetic approaches towards materials
based on organogermanium compounds and their practical use. In the first contribution, “Oligo- and Polygermanes”,
Charles S. Weinert (Oklahoma State University, Stillwater, USA) reviewed and updated the recent advances in the field of
the oligo- and polygermanes, discussing general synthetic methods for their preparation and also their peculiar physical
properties (luminescence, electrochemistry). In the very final chapter of the Applications part (and the whole book)
“Bioorganic and Medicinal Organogermanium Chemistry”, Takashi Nakamura, Yasuhiro Shimada, and Katsuyuki Sato
(Asai Germanium Research Institute, Hakodate, Japan) give an account on the production and use of bioactive organoger-
manium compounds (such as Ge-132) in medicinal chemistry.
As an editor of the volume, I highly appreciate the works of all above-mentioned authors whose excellent contributions
will hopefully turn this book into a guide to contemporary organogermanium chemistry and a useful reference source, to
further inspire those already working in the field and to attract newcomers to join the fascinating world of organogerma-
nium compounds. Although the book is primarily and foremost addressed to specialists in the field of organogermanium
and organometallic chemistry, it could also be of interest to both Main Group and transition metal chemistry experts, as
well as to computational and material science chemists, and to the rest of the chemical community, including undergrad-
uate, graduate, and post-graduate students of the advanced levels.
Vladimir Ya. Lee (Editor)

University of Tsukuba, Tsukuba, Japan
April 2022
xiii
List of Contributors
Yitzhak Apeloig Miriam Karni

Schulich Faculty of Chemistry Schulich Faculty of Chemistry
Technion-Israel Institute of Technology Technion-Israel Institute of Technology
Haifa, Israel Haifa, Israel
Frank Breher Tanja Kunz

Institute of Inorganic Chemistry Institut für Anorganische Chemie
Karlsruhe Institute of Technology (KIT) Universität Tübingen
Karlsruhe, Germany Tübingen, Germany
Mikhail P. Egorov Alexander A. Korlyukov

N. D. Zelinsky Institute of Organic Chemistry Pirogov Russian National Research Medical University
Moscow, Russia Moscow, Russia
Vladimir Ya. Lee

Heinz Gornitzka
Department of Chemistry
Laboratoire de Chimie de Coordination du CNRS
University of Tsukuba
Université Toulouse
Tsukuba, Japan
Toulouse, France
William J. Leigh
Catherine Hemmert Department of Chemistry & Chemical Biology
Laboratoire de Chimie de Coordination du CNRS McMaster University
Université Toulouse Hamilton, Ontario, Canada
Toulouse, France
Christoph Marschner
Alexander Hinz Institut für Anorganische Chemie
Institute of Inorganic Chemistry Technische Universität Graz
Karlsruhe Institute of Technology (KIT) Graz, Austria
Karlsruhe, Germany
Yoshiyuki Mizuhata
Viatcheslav V. Jouikov Institute for Chemical Research
N. D. Zelinsky Institute of Organic Chemistry Kyoto University
Moscow, Russia Kyoto, Japan
Naokazu Kano Thomas Müller

Department of Chemistry Institute of Chemistry
Gakushuin University Carl von Ossietzky University Oldenburg
Tokyo, Japan Oldenburg, Germany
xiv List of Contributors
Takashi Nakamura Sakya S. Sen

Asai Germanium Research Institute Co., Ltd. Institute of Inorganic Chemistry
Hokkaido, Japan Georg-August-University Göttingen
Göttingen, Germany
Norio Nakata
Department of Chemistry Yasuhiro Shimada
Saitama University Asai Germanium Research Institute Co., Ltd.
Saitama, Japan Hokkaido, Japan
Mikhail A. Syroeshkina
Vadim V. Negrebetsky
N. D. Zelinsky Institute of Organic Chemistry
Pirogov Russian National Research Medical University
Moscow, Russia
Moscow, Russia
Norihiro Tokitoh
Elena N. Nikolaevskaya Institute for Chemical Research
N. D. Zelinsky Institute of Organic Chemistry Kyoto University
Moscow, Russia Kyoto, Japan
Kohtaro Osakada Ana Torvisco

Chemical Resources Laboratory Institute for Inorganic Chemistry
Tokyo Institute of Technology Graz University of Technology
Yokohama, Japan Graz, Austria
Herbert W. Roesky Frank Uhlig

Institute of Inorganic Chemistry Institute for Inorganic Chemistry
Georg-August-University Göttingen Graz University of Technology
Göttingen, Germany Graz, Austria
Charles S. Weinert
Katsuyuki Sato
Department of Chemistry
Asai Germanium Research Institute Co., Ltd.
Oklahoma State University
Hokkaido, Japan
Stillwater, Oklahoma
Andreas Schnepf Kirill V. Zaitsev

Institut für Anorganische Chemie Department of Chemistry
Universität Tübingen Moscow State University
Tübingen, Germany Moscow, Russia
1
Computational and Theoretical Aspects of Structure and Bonding in Doubly

Bonded Organogermanium Compounds

Schulich Faculty of Chemistry, Technion - Israel Institute of Technology, Haifa, Israel
In memory of Professor Robert (Bob) West, a pioneer in main group chemistry and group 14 compounds in particular, and
a unique human being.
List of Abbreviations
1-Ad 1- adamantyl
AIM atoms in molecules
Ar aryl
B3LYP Becke, 3-parameter, Lee–Yang–Parr functional
Bbt 2,6-[CH(SiMe3)2]2-4-[C(SiMe3)3]-C6H2
BDE bond dissociation energy
CCSD(T) coupled cluster, singles, doubles (triples)
CDA charge delocalization analysis
CGMT Carter-Goddard-Malrieu-Trinquier model
CV cyclic voltammetry
Dip (or Dipp) 2,6-iPr2-C6H3
DMAP 4-Dimethylaminopyridine
Dmp 2,6-dimethylphenyl
DSSE divalent state stabilization energy
EDA energy decomposition analysis
Eind 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl
EMind 1,1,7,7-tetraethyl-3,3,5,5-tetramethyl-s-hydrindacen-4-yl
EPR electron paramagnetic resonance
Etind
Et Et
Et Et
HOMO highest occupied molecular orbital

LDA/NL local density approximation with non-local corrections
LDF London Dispersion Forces
LUMO lowest unoccupied molecular orbital
Mes 2,4,6-Me3-C6H2
Mes* 2,4,6-tBu3-C6H2
NBO natural bond orbital
NHC N-Heterocyclic carbene
NICS nucleus independent chemical shift
NMR nuclear magnetic resonance
NPA natural population analysis
NRT natural resonance theory
PES potential energy surface
Organogermanium Compounds: Theory, Experiment, and Applications, Volume 1, First Edition. Edited by Vladimir Ya. Lee.
© 2023 John Wiley & Sons, Inc. Published 2023 by John Wiley & Sons, Inc.
2 1 Computational and Theoretical Aspects of Structure and Bonding in Doubly Bonded Organogermanium Compounds
RRKM Rice-Ramsberger-Kassel-Marcus theory

SDD Sttutgart-Dresden Double zeta Electron Core Potential (ECP)
SOJT second-order Jahn Teller
Tbb 2,6-[CH(SiMe3)2]2-4-tBu-C6H2
Tip 2,4,6-triisopropylphenyl
VB valence bond
WBI Wiberg bond index
Xylyl (CH3)2C6H3
1.1 Introduction
Unsaturated hydrocarbons having C=C double bonds; heteroelement- substituted doubly bonded carbon compounds, e.g.,
ketones; alkynes with C≡C triple bonds; hydrocarbons with an extended number of double bonds, such as dienes and
allenes; all are of fundamental importance to chemistry and the chemistry of life. In contrast stable heavier group 14 ana-
logues, with Si, Ge, Sn and Pb atoms, were believed to be nonexistent until several decades ago (see below the historical
overview). The last four decades have witnessed an enormous progress in the synthesis and in the theoretical under-
standing of the properties of these groups of compounds. The experimental progress was accompanied, and in many cases
even preceded, by theoretical and computational studies. These advances were enabled by two important developments:
(a) the substantial advances in quantum mechanical computational methodology [1–10] that now enables reliable, accu-
rate and efficient calculations of the properties of relatively large molecules possessing heavy elements. These develop-
ments make quantum chemical calculations a reliable tool for the quantitative analysis of chemical phenomena and a
reliable guide to experiment; and (b) the dramatic developments in computer technology that have accelerated calculations
dramatically [11, 12].
The synthesis, molecular structure determination, physical and chemical properties, and the development of bonding
models of multiply bonded compounds of heavier group 14 elements, Si, Ge, Sn and Pb, have been reviewed extensively in
the past three decades [13–26]. The numerous experimental and theoretical studies carried out in this field have revealed
fundamental differences in the structures, physical properties and chemical behavior between carbon multiply bonded
compounds and analogous group 14 heavier congener compounds. The heavier group 14 compounds were considered
“unusual”. In contrast, Kutzelnigg suggested that the heavier main group element compounds have “regular” behavior,
while carbon compounds are the exception [27]. This revolutionary view is now widely accepted by main group researchers
(not only for group 14 elements). The trends in the physical properties of group 14 elements, E, are largely responsible for
the unprecedented structures and chemical behavior of the heavier group 14 compounds compared to those of the analo-
gous carbon compounds. Selected properties of group 14 elements are given in Table 1.1. A comparison of the important
physical properties of group 14 elements was also provided by Basch and Hoz [28]. The effects of the trends in the prop-
erties of the E atoms shown in Table 1.1, on the structure and nature of bonding of group 14 multiply bonded compounds,
are discussed in section 1.4.1.
The unusual structures and bonding motifs of multiply bonded heavier group 14 molecules attracted the attention of
many theoreticians, who studied their molecular structures, nature of bonding, kinetic and thermodynamic stability,
potential energy surfaces for a variety of their reactions, etc. Many of these theoretical studies were carried out before stable
compounds of these classes were synthesized, and were therefore truly predictive, and in some cases directed experiment.
Two comprehensive reviews on the theoretical studies of the chemistry of organic Si, Ge, Sn and Pb compounds were pub-
lished: one by Apeloig, Karni and Schleyer in 2001 [44] and one in 2002 by Frenking and coworkers [45].
In this chapter we review the theoretical studies of doubly bonded organogermanium compounds, mainly those
published in the years 2000–2020 but occasionally we added important studies published in 2021. We have highlighted
the insights that these theoretical studies provide on molecular structures, nature of bonding, stability vs. isomeric forms,
and the physical properties, of these intriguing compounds. We do not include in this review their reactions and reaction
mechanisms. Where available, we relate and compare the computational results to reported experimental studies. In our
view, it is important to examine organogermanium compounds in comparison to their closest neighbors in the Periodic
Table, Si and Sn. Thus, when available, we discuss comparisons with analogous organosilicon compounds (the element
most similar to germanium) and other group 14 elements, mainly Sn. For pre-year 2000 theoretical studies, the readers
are referred to the above-mentioned reviews [44, 45] and to specific papers cited in this chapter.
1.2 Computational Methods 3
Table 1.1 Selected physical properties of group 14 elements.
E C Si Ge Sn Pb References
Electronegativity
Allred-Rochow 2.50 1.74 2.02 1.72 1.55 [29,30]
Pauling 2.55 1.90 2.01 1.96 2.33 [31]
Allen
2.54 1.92 1.99 1.82 – [32]
Atomic and ionic radii (pm) 77 118 121 140 175a [33–36]
Neutral 16 40–42 73 93 118–120
2+ 53 69–71 78–84
4+
Valence orbital energy (eV) −19.39 −14.84 −15.52 −13.88 −15.41 [37]
s −11.07 −7.57 −7.29 −6.71 −6.48
p 8.32 7.27 8.23 7.17 8.93
Energy difference
Δr = (rp − rs) (pm)b −0.2 20.3 24.9 28.5 35.8 [37]
Ionization energy (eV) 16.60 13.64 14.43 13.49 16.04 [38–40]
nsc 11.26 8.15 7.90 7.39 7.53
npd
Electron affinity (eV) 1.26 1.76 1.81 1.68 1.91 [41]
Hybridization of E in EH4e sp3.17 sp2.08 sp2.05 sp1.79 sp1.75 [42]
f
Hybridization of E in H2E=EH2 (C2h)
σ(E-E) sp2 sp1.79 sp2.07 sp2.22 sp2.52 [43]
“π(E=E)” p sp18.0 sp7.40 sp5.78 sp3.82
a
Metallic distance;
For the transition: ns2np2(3P) → ns1np2(4P);

b
Difference of orbital radii between the valence p and s orbitals;
For the transition: ns2np2(3P) → ns2np1(2P);

c
d
e
Calculated using NBO analysis;
f
Calculated using NBO analysis at B3LYP/6-31++G(d,p).
The theoretical literature of organogermanium compounds is vast. When we collected the literature for this review, we
were amazed how vast is this field, and because of space limitations we had to limit the scope of this review, which even so
includes more than 540 references! In this chapter, we concentrate on doubly bonded organogermanium compounds,
which in their bonding and other fundamental properties are significantly different from analogous carbon compounds.
We discuss homonuclear and heteronuclear organogermanium compounds, R2Ge=ER2, E=C, Si, Ge, and extended doubly
bonded organogermanium compounds such as germadienes, germaallenes, and germaaromatic derivatives, i.e., germ-
abenezene analogues. For lack of space, we do not discuss doubly bonded compounds between group 14 elements and
groups 13, 15 and 16 elements or triply bonded compounds.
For completeness, we present a brief historic overview of the field, since the isolation of the first stable doubly bonded
heavier group 14 element compounds in 1976.
1.2 Computational Methods
For the benefit of readers unfamiliar with the theoretical methods and terms, we bring a brief overview of the theoretical
methods that are currently frequently used in theoretical calculations of organogermanium compounds. Details of the
specific computational methods or of the basis sets mentioned in this review can be found in the cited papers.
The rapid development of computational packages for electronic structure calculations in the last three decades has been
recently reviewed [10] (for a comprehensive list of available software packages see Ref. [46]). These computational soft-
ware packages apply state-of-the-art theoretical methods for electronic structure modelling of molecules in the gas phase,
solution, and the solid-state. Currently, these software packages apply mainly two theoretical approaches, ab initio wave-
function based molecular orbital (MO) methods [1–5], and electron density based Density Functional Theory (DFT)
methods [6–8]. These software packages enable highly reliable calculations of molecular structures, potential energy sur-
faces, electron density and population analysis, vibrational frequencies, UV-Vis, NMR, EPR, IR and Raman spectroscopic
properties, electronic circular dichroism (ECD), excitation energies, and other properties [1–9, 47].
Below we briefly summarize the theoretical approaches most commonly used for the calculation of the above-mentioned
molecular properties. A detailed description of the field is given in the monographs cited above. Specific definitions and
description of the computational methods used in the studies reviewed in this chapter are provided in the cited papers and
references therein.
1.2.1 Ab initio Methods

Ab initio MO methods are based on Hartree-Fock (HF) self-consistent field (SCF) calculations, in which the total multi-
electron wave function Ψ is composed from single electron spin orbital wave functions ϕl (MO) via a single anti-symme-
trized determinant (the Slater determinant). The single electron wave functions are expressed by a sum of basis functions
(basis sets). A very large choice of basis sets exists; they differ in size and in their adaptation for a specific calculated
property [48, 49]. In addition to choosing the appropriate computational method, a correct choice of a basis set deter-
mines the computational accuracy and efficiency. However, even with the largest basis set and reaching the HF limit,
the HF method recovers only 95–99% of the total energy. The missing fraction is relatively small in absolute terms, but
most chemistry happens in this small remaining fraction. The missing fraction is corrected by including electron corre-
lation energy.
The most frequently used methods for including electron correlation are by perturbation theory, i.e., Møller-Plesset [50]
in the nth order, (MPn) [51], configuration interaction (CI) [52], and coupled-cluster (CC) [53] methods [1–5, 46]. Today,
coupled-cluster methods provide the most accurate results among the practical ab initio electronic structure theories and
often serve as a benchmark for evaluating, in the absence of experimental results, the reliability of new computational
methods, e.g., density functionals. Ab initio methods can be improved systematically by increasing the size of the basis sets
and the amount of correlation energy that is included. It is assumed that with a complete basis set and full CI the exact
solution to the Schrödinger equation can be obtained. However, the major drawback of these methods is the large com-
puter resources required, and they are therefore applicable only to moderately-sized molecules.
1.2.2 Density Functional Theory ( DFT) Methods

DFT methods [6–8], which include electron correlation indirectly, have become the most popular electronic structure
methods in computational chemistry over the last 30 years. Recent advances in the development of density functionals
(DF) allow one to reliably describe numerous properties of large systems at an affordable computational expense. A major
difficuly in developping reliable DFs is that in contrast to the rigor of ab intio methods, DFT methods do not allow systematic
improvement of the theoretical method. The strategy for improving DFs is by adding new ingredients and parametrizing
them by fitting to a set of properties, e.g., atomization energy, thermochemistry, barrier heights, etc. For example, addition
of a small percentage of exact HF exchange (i.e., hybrid DFs) improves significantly the performance of local DFs as shown
in Figure 1.1. For example, the performance of the PBE (Perdew–Burke-Ernzerhof) functional is improved by a factor of
two in PBE0, which mixes the PBE exchange energy with 25% exact Hartree–Fock exchange energy [8, 54]. Figure 1.2
shows the importance of including London dispersion corrections (D2 [55] and D3(BJ) [56]) that capture noncovalent
interactions more effectively. Based on an assessment of 200 DFs tested on 84 data sets including thermodynamic data,
isomerization energies, barrier heights, etc., it was concluded that addition of dispersion corrections should be applied with
caution [8]. Recommendations for effective use of DFs that are suited for specific applications are given in Refs. [8] and
[57], and the reader is advised to consult these references before applying a specific method to his own research or when
evaluating the research of others. As can be seen in Figures 1.1 and 1.2, calculated errors can be very large, e.g., with BLYP,
B3LYP, and BP86.
The common notations of the theoretical methods used in the literature are the following: each computational level (ab
initio and DFT) is defined by the type of method and the basis sets which are used. By convention, the computational level
is designated as follows: [method 1/basis set 1]//[method 2/basis set 2]. Method 2 and basis set 2 are those used for geom-
etry optimizations while method 1 and basis set 1 are those used for obtaining the final energy or other properties that are
calculated.
1.2 Computational Methods 5
30
NCD ID BH
25
RMSD (kcal/mol)
20
15
10
0
BLYP B3LYP BP86 B3P86 PBE PBE0 revPBE revPBE0 TPSS TPSSh revTPSS revTPSSh
Figure 1.1 Stacked root-mean-square deviations (RMSD, in kcal/mol) for a set of six popular local/hybrid pairs (e.g., BLYP/B3LYP,
BP86/B3P86, etc.) derived from 155 isomerization energies (ID), 206 barrier heights (BH), and 91 noncovalent (NCD) interactions.
Reproduced with permission from Ref. [8]. Copyright (2017) Taylor and Francis, Ltd.
6
NCED IE
5
RMSD (kcal/mol)
0
BLYP -D2 -D3(BJ) B3LYP -D2 -D3(BJ) TPSS -D2 -D3(BJ) TPSSh -D2 -D3(BJ)
Figure 1.2 Stacked root-mean-square deviations (RMSD, in kcal/mol) for a set of four DFs and their dispersion corrected (D2 and
D3(BJ)) counterparts. Based on 1744 non-covalent dimer interactions (NCED) and on 755 isomerization energies (IE). Reproduced with
permission from Ref. [8]. Copyright (2017) Taylor and Francis, Ltd.
1.2.3 Methods for Analysis of Electronic Structure

Important information and deeper insight into the chemical and physical properties of the studied molecules can be gained
by analyzing their wave function, the electron distribution, hybridization at various atoms, the nature of the chemical bond,
etc. Several analysis methods are mentioned throughout this chapter. The most popular is the Natural Bond Orbital method
(NBO) [58–63] that calculates the Natural Population Analysis charges (NPA). The NPA charges are believed to be more
accurate [64, 65] than the Mulliken atomic charges [66, 67], which are still often used. Several other methods for calculating
atomic charges are available and a comparison of their accuracy for specific purposes was discussed, e.g., in References [64]
and [65]. NBO analysis, based on localized orbitals, provides a Lewis structure of the molecule, bond orders, hybridization
at the various atoms, and suggests possible resonance structures that contribute to the molecular electronic structure and
their relative weights (NRT)[68], thus providing important information for analyzing the structures and bonding of the
studied molecules. Other frequently used computational procedures are: (a) Atoms in Molecules (AIM), developed by Bader
[69], which is based on a topological analysis of the electron density in atomic basins, and calculates also atomic AIM
charges; and (b) Energy Decomposition Analysis and Natural Orbitals for Chemical Valence (EDA-NOCV), which proved to
be a powerful tool for bonding analysis. For a detailed description of the above-mentioned methods and their performance,
the reader is referred to the recent review by Frenking, Schwerdtfeger, and coworkers [70].
1.2.4 How Important are Relativistic Effects for Ge?

As the nuclei become heavier the strong attraction of the electrons by the heavier nuclear charge causes the electrons to
move faster and behave relativistically [71, 72], i.e., their relative mass increases and the effective Bohr average radius for
(a) (b)
–12.0
nonrelativistic energy
Bond length relative to NR (a.u)

–14.0 0.02
0
s orbital energy (eV)
–0.02
relativistic energy
–16.0
–0.04
–0.06
–0.08
–18.0
CH4 SiH4 GeH4 SnH4 PbH4
–20.0
C Si Ge Sn Pb
Figure 1.3 (a) Stabilization of the ns valence orbital due to relativistic effect. Reprinted from Ref. [73] by permission of Gordon and
Breach science publishers, 1999; (b) The contraction of the E–H bond length of EH4 (E=C, Si, Ge, Sn and Pb) calculated using Fock-
Dirac (rectangle) and Fock-Dirac-Breit (*) relativistic approaches relative to non-relativistic calculations. Reprinted with permission
from Ref. [74]. Copyright (1992) Springer Verlag.
the inner-electrons contracts. It was found that the relativistic contraction of the 1s orbital of Ge, Sn, and Pb, is 3, 8, and
20%, respectively [71]. Due to the orthogonality of the higher ns orbitals to the 1s orbital, the relativistic effect on higher ns
orbitals is similar [71].
As shown in Figure 1.3a, the relativistic effect stabilizes the ns orbitals of Ge–Pb atoms. However, the effect for Ge is
relatively small [73]. The relativistic contraction of the E–H bond in EH4 is 0.01% for CH4, 0.05% for SiH4, 0.37% for GeH4
1.16% for SnH4, and 3.9% for PbH4, leading to nearly identical E–H bond lengths in SnH4 (1.734 Å) and PbH4 (1.737 Å).
These data show relatively small relativistic effects for Ge, and consequently most calculations of Ge compounds do not
include relativistic effects.
1.3 Historical Overview
Until the early 1970s, compounds with heavier group 14 elements, E, having double and triple bonds, were unknown (i.e.,
homonuclear or heteronuclear compounds possessing E=E’ double bonds and E≡E’ triple bonds (E, E’=Si, Ge, Sn, and Pb;
E’=group 13–16 elements). Many experimental failures [75–78] to synthesize such compounds and some theoretical studies
[79, 80] led to formulation of the classical “double bond rule” stating that “elements having a principal quantum number
greater than 2 should not be able to form (p–p) π bonds with themselves or with other elements” [81]. Therefore, this group
of compounds were believed not to exist. However, the pursuit for such compounds continued, leading in the late 1970s to
early 1980s to detection of transient intermediates having E=E’ bonds of heavier group 14 elements [22, 75–78, 82, 83]. The
first important breakthrough occurred in 1976, interestingly in germanium and tin chemistry, with the synthesis, isolation,
and characterization of alkyl substituted digermene and distannene, [(Me3Si)2CH]2E=E[CH(SiMe3)2]2, (E=Ge (1) and
E=Sn, (2)) by Lappert and coworkers [84–87]. The X-ray structure of digermene 1 shows a Ge–Ge bond length of 2.347 Å
[86, 87], significantly shorter than the single Ge–Ge bond length of 2.463 Å in (GePh2)6 [87]. The Ge atoms in 1 are pyramidal
featuring a trans-bent structure with sum of angles around Ge, Σ∠(Ge) = 348.5°, and a trans-bent angle of 32°. The X-ray
structure of 2 [84, 85] revealed a Sn–Sn bond distance of 2.764 Å, similar to typical Sn–Sn single bond distances of 2.78–
2.82 Å [44, 87], and pyramidal Sn atoms, Σ∠(Sn) = 342°, and a trans-bent angle of 41.6°. The twist angle around the
1.3 Historical Overview 7
double bond in both 1 and 2 is 0°. Based on these geometries, the authors suggested that 1 and 2 result from a double
donor-acceptor interaction of two singlet 1A1 ER2 monomers, in which the filled lone-pair orbital on one E(II) atom
donates electrons into the vacant p orbital of the second E(II) monomer (Scheme 1.1, for E=Sn). However, 1 and 2
were stable only in the solid state, while in solution they dissociate to their corresponding monomers [87]. (tBu2MeS
i)2Sn=Sn(SiMetBu2)2 synthesized in 2004 by Sekiguchi et al. [88] was the first, of only few isolated distannenes, that
are stable also in solution [15, 89].
Sn Sn Sn Sn
C2h
Lone-pair donation
Scheme 1.1 Mode of interactions of two stannylenes producing a trans-bent distannene.
In 1981, in two milestone papers, Brook and West and their coworkers reported independently the syntheses, isolation,
and characterization, including by X-ray crystallography, of the first stable silene, (Me3Si)2Si=C(OSiMe3)1-Ad (3) [90–92]
and disilene, Mes2Si=SiMes2 (4), [93–96], respectively. Silene 3 has a planar skeleton with a Si=C bond length of 1.764 Å,
(r(Si-C) = 1.869 Å in H3CSiH3 [97]). In disilene 4, r(Si=Si) = 2.143 Å (r(Si-Si) = 2.327 Å in H3SiSiH3 [97]), and the Si centers
are slightly pyramidal with Σ∠(Si) = 358° and a trans-bent angle of 12°.
Since these pioneering landmark achievements, this field has witnessed an enormous progress. The key point to success
is the use of large bulky substituents that protect the highly reactive E=E’ double bonds from further reactions. Stable com-
pounds with a variety of E=E and E=E’ bonds (E, E’=Si, Ge, Sn, Pb; E’=group 13–16 elements), as well as compounds
having an extended number of conjugated double bonds, i.e., heavier allenes and butadiene analogues, and heavier benzene
analogues, were synthesized, isolated, and characterized and their chemistry has been reviewed extensively [16, 18, 24,
98–100].
Heavy alkyne analogues RE≡ER (E=Si, Ge, Sn) have also been isolated, but they are much less abundant than heavy
doubly bonded compounds [17, 18, 24]. Unlike the linear alkynes, all known heavy alkynes have a highly trans-bent
geometry [17, 18, 24]. The first digermyne ArGe≡GeAr (5) and distannyne ArSn≡SnAr (6) [Ar = 2,6-(2,6-iPr2-C6H3)2-
C6H3], were reported by Power and coworkers in 2002 [101]. Several digermynes and distannynes with other substitu-
ents on the aryl groups were reported by these authors in 2010 [102]. In 2006, Tokitoh et al. reported the synthesis of
BbtGe≡GeBbt (7) (Bbt = 2,6-[CH(SiMe3)2]-4-[C(SiMe3)3]-C6H2) [103]. The synthesis and characterization by X-ray crys-
tallography of the first stable disilyne RSi≡SiR, R=[SiiPr{CH(SiMe3)2}2] (8) was reported by Sekiguchi’s group in 2004
[104, 105]. Wiberg reported earlier the detection of a relatively stable disilyne, RSi≡SiR, R=SiMe(Sit-Bu3)2 (9), but its
crystal structure could not be obtained [106]. A second known stable disilyne with R = Bbt (10) was reported in 2008 by
Tokitoh’s group [107, 108]. In 1999, Schwarz and Apeloig reported the identification of two silynes HC≡SiX (X=F, Cl) in
neutralization–reionization mass-spectrometric experiments, and demonstrated their microsecond existence under
high-vacuum conditions [109]. More recently, Kato and Baceiredo reported a base stabilized silyne that was stable up to
−30°C. Its X-ray structure revealed a short Si–C bond length of 1.667 Å, indicating the possible existence of a Si–C triple
bond [110, 111]. Germa- [112] and stanna [113]-acetylenes were identified only as intermediates in a low-temperature
matrix or by their trapping reactions [113]. To date, efforts to synthesize isolable E≡C (E=Si, Ge, Sn) triply bonded mol-
ecules were not successful.
It should be emphasized that all known stable multiply bonded heavier alkene and alkyne analogues are substituted with
very bulky substituents that stabilize them kinetically, preventing their dimerization and significantly slowing their other
reactions. Theoretical studies in the last decade pointed to the importance of attractive noncovalent London Dispersion
Forces (LDF) [114] between the bulky substituents, in stabilizing these weakly bonded multiply bonded molecules against
dissociation to their tetrylene monomers [115–118].
In Table 1.2 we provide a list of characterized doubly bonded germanium compounds and some of their important
geometric parameters (both homo- and heteronuclear) that were synthesized since 2010 and not covered in the reviews of
Power [18] and Lee [24]. Table 1.2 also includes, where available, the results of theoretical calculations of these com-
pounds’ structures.
Table 1.2 Doubly bonded organogermanium compounds, R2Ge=E’R’2, reported in 2010–2020.
Twist angle UV-Vis

Compound Ge=E’ (Å) Σ∠(Ge); Σ∠(E’) (°) around Ge=E’ absorption (nm) Reference Publication year
a) Digermenes
11 (tBuMe2Si)2Ge=Ge(SiMe2tBu)2a 2.270 0.3b 7.5 362, 421 [119,120] 2010
12 (tBu2MeSi)2Ge=Ge(SiMetBu2)2a 2.346 358.8 52.8 618 [121a,b] 2011, 2014
R2Ge=GeR2 (calculated)c 2.278 334.0 0.5 3.11d [121b]
a) R = H3Si 2.284 335.1 13.5 2.75d
b) R = Me3Si
2.347 358.7 55.3 2.21d
c) R = tBu2MeSi
13 R R Cl R
Si Si Xyl
N C Ge Ge C N
334.5
Xyl Si Si 2.294 No twist 507 [122] 2015
37.7b
R Cl R R
R = Tip = 2,4,6-iPr3C6H2,
Xyl = 2.6-Me2C6H3
14 R2Ge2=Ge1RSiPh3 346.53(Ge1)e
R = Tip = 2,4,6-iPr3C6H2 2.328 345.24 (Ge2)f 13.6 426 [123] 2019
15 R2Ge=GeRSiMe2Cl
R = Tip = 2,4,6-iPr3C6H2 –g – – 435 [123] 2019
16 R2Ge=GeRSiMePhCl
R = Tip = 2,4,6-iPr3C6H2 – – – NA [123] 2019
17 R2Ge=GeRSiMe2Ph
R = Tip = 2,4,6-iPr3C6H2 – – – 424 [124] 2018
18 R2Ge=GeRSiMe3
R = Tip = 2,4,6-iPr3C6H2 – – – 424 [124] 2018
19 R2Ge2=Ge1RLi · 2dme
7.1 (Ge1)b
R = Tip = 2,4,6-iPr3C6H2,
dme = 1,2-dimethoxyethane 2.284 12.8 (Ge2)b 19.9 435 [124] 2018
20 K22+[(boryl)Ge=Ge(boryl)] 2–
Boryl = (HCDippN)2B,
Dipp = 2,6-iPr2C6H3h 2.392 – – NA [125] 2016
Twist angle UV-Vis
21 R2Ge2=Ge1R(C(R’) = O)
476 (Ge=Ge)
R = Tip = 2,4,6- iPr3C6H2; R’ = (a) tBu, (b) – – – [123] 2019
and 386 (C=O)i
2-methylbutan-2-yl and (c) 1-adamantyl
22 (E)-(L)HGe=GeH(L)
322.5
L = N(SiiPr3)R 2.486 No twist 460 [126] 2013
54.1b
R = 2,6-[CHPh2]-4-iPrC6H2
23 (E)-(L)HGe=GeH(L) 2.535 344.8 No twist NA [127] 2019
Dip
N
39.1b
SiMe3
L= B
N
N
Dip
Dip=Diisopropylphenyl
toluene/18-crown-6
24 (E)-(Eind)XGe=GeX(Eind) (a) 2.415 (a) 337.1, 43.29b No twist (a) 406 [128] 2018
j
X= (a) Br and (b) Cl (b) 2.412 (b) 335.9, 44.34b (b) 390
Et Et Et Et
Et Et
Et Et
Eind
25 ArBrGe=GeBrAr a) 2.509 a) 44.6b a) No twist b) 449 [129,130] 2005,

a) Ar = Bbt = 2,6-[CH(SiMe3)2]2-4- b) 2.406 b) 336.3 2016
[C(SiMe3)3]-C6H2
b) Ar = Tbb = 4-tBu-2,6-[CH(SiMe3)2]2-C6H2
26 Bbt r(Ge=Ge) = 2.413 – 494 [131] 2015

Bbt
C(Bbt) = 133.6
∠C(Bbt)-Ge-Ge-
r(C-C) = 1.532
Ge Ge 39.5b
Bbt = 2,6-[CH(SiMe3)2]-4-[C(SiMe3)3]-C6H2
(Continued)
Table 1.2 (Continued)
Twist angle UV-Vis

27 Bbt Bbt 2.414 – NA [132] 2018

Ge–C(Bbt) = 134.1
∠C(Bbt)–Ge–
Ge Ge
36.1/43.0b
Ph
28 Tbb Tbb r(Ge=Ge) = 2.416 351.3 – 369 [130] 2016

Ge Ge r(C=C) = 1.362
Ph Ph
Tbb=4-tBu-2,6-[CH(SiMe3)2]2-C6H2
29 EMind 2.430 Ge1/Ge3 360 – 458, 510 [133] 2018

1 Ge2 334
Ge
Ge4 328
EMind 4 Ge2 EMind
Ge
Ge3
EMind
Et Et Et
Et
Me
Me Me Me
EMind
b) Compounds with Ge=E’ bonds

i) Ge=C bonds
30 SiMe3 2.039k 286.6k,l 88.3l,m NA [134,135] 2019

NiPr2
Me
Ge C
Me
NiPr2
SiMe3
Twist angle UV-Vis
31 Se 1.921 (Ge-C) 339.9, 338.7 536 [136] 2018

Tbb Tbb
∠SeGeCC = 11.6
Ge Ge 1.375 (C-C)
Ph Ph
32 1.998n 310.5 (Ge) 18.5 NA [137,138] 2017, 2020
359.8 (C)
R O
33 b) 2.007; b) 304.6 (Ge), – a) 442; b) 463; [138,139] 2015, 2020
K
c) 2.036 359.9 (C); c) 422
Ge
Me2Si SiMe2 c) 310.7 (Ge), 359.9 (C)
Me2Si SiMe2
Ge
Me3Si SiMe3
Toluene/18-crown-6
o p
a) R = Mes; b) R = o-Tol ; c) R = 1-Ad
34 a) 2.055 a) 314 (Ge) – a) 447 [140] 2020

r(C-O) = 1.252 359.6 (C) b) 420
b) 2.047 b) 314.5 (Ge1)
r(C-O) = 1.248 298.2 (Ge2)
359.6 ( C)
Toluene/18-crown-6
a) R=Mes; b) R=1-Ad
35 R O 1.835 351.7 (Ge), – 368 [138,139] 2015, 2020
SiMe3 (r(C = O) = 1.388) 360.0 (C)
Ge
Me2Si SiMe2
Me2Si SiMe2
Ge
Me3Si SiMe3 R = Mes
(Continued)
Twist angle UV-Vis

ii) Ge=Si bonds

36 (tBuMe2Si)2Ge=Si(SiMe2tBu)2 2.221 0.6b 7.5 359, 413 [119] 2010
Tip Tip
37 r(Ge=Si) = 2.246 – planar 495 [141] 2021
Si r(Ge-K) = 3.407 4-membered ring
N C Ge K •18-crown-6
Xyl Si
Tip
iii) Ge=E’ (E’=group 13, 15 and 16

elements)
38 Ph2 1.886 X=Cl: 359.6 (Ge), – NA [142] 2020
P 360.0 (B)
B X
Ge
X= Cl, Br Ar*=2,6-Tip2-C6H3 (Tip=2,4,6-iPr3C6H2)
39 Dipp Dipp r(Ge1-P1) = 2.266, – – NA [143] 2016

N N r(Ge1-P2) = 2.272
P1
Ge1 Ge2
N P2
N
Dipp Dipp
Dipp=2,6-iPrC6H3
40 (tBu2MeSi)2Ge=As-Mes* 2.273 360.0 planar 390q, 450r [144] 2018

Mes* = 2,4,6-tBu3-C6H2
41 Eind2Ge=O 1.647 359.8 planar 297 (IR (Ge=O) [145,146] 2012
916 cm−1)
Twist angle UV-Vis
42 1.672s 333.9s – NA [147] 2009
N N
R R
Ar
N Ge O
N
Ar
R = Me, iPr; Ar = 2,6-iPr2C6H3
43 1.646 343.6 – NA [148] 2011

N
N
Ar
N Ge
O
N
Ar
Ar = 2,6-iPr2C6H3
Ar
44 2.077 338.5 – NA [149] 2004
N
S
Ge
N OH
Ar
Ar = 2,6-iPr2C6H3
45 Ar S 2.095 – – NA [150] 2017

N Ge
PCy2
N
Ar
Ar = 2,6-iPr2C6H3; Cy = C6H11
46 Ar S1 S3 2.068 – – NA [150] 2017

(Ge-S2) = 2.234
N Ge PCy2
S2
N
Ar
Ar = 2,6-iPr2C6H3
(Continued)
Twist angle UV-Vis

47 Ar Se 2.221 – – NA [150] 2017

N Ge
PCy2
N
Ar
Ar = 2,6-iPr2C6H3
48 Ar Se 2.163 – – NA [150] 2017

N Ge
P(SiMe3)2
N
Ar
Ar = 2,6-iPr2C6H3
c) Extended doubly bonded compounds
49 2.268, 2.290t, u – – 451 [151] 2017
BbtGe GeBbt
Si
Bbt = 2,6-[CH(SiMe3)2]-4-[C(SiMe3)3]-C6H2
d) Germabenzenes
50 Tbb Tbb 2.312 345.3 – 383 [152] 2015

Ge Ge
Tbb = 4-tBu-2,6-[CH(SiMe3)2]2-C6H2
Twist angle UV-Vis
51 R1 R1 r(Ge-C1) = 1.890v 357.3v – 442v [153] 2019

C1 C2 r(Ge-C3) = 1.866v
Tbb Ge Ge Tbb
C3 C4
R2 R3
a) R1 = R2 = R3 = Ph
b) R1 = R2 = R3 = Et
c) R1 = Ph, R2 = Me, R3 = nPr
Tbb = 4-tBu-2,6-[CH(SiMe3)2]2-C6H2
a
A preliminary X-ray diffraction – poor refinement;
b
trans-bent angle;
c
At B3LYP/6–31G(d);
d
HOMO-LUMO gap in eV;
e
Trans-bent angle = 23.7°;
f
Trans-bent angle = 21.3°;
g
Unavailable data; X-ray crystal structure could not be obtained. Characterized as digermenes by their NMR spectra;
h
For previously synthesized digermene dianions, see Ref. [46] cited in Ref. [125] [Pu, L. et al. J. Am. Chem. Soc., 1998, 120, 12682–12683]. For a review, see: Wang, Y. and Robinson, G. H. Chem.
Commun., 2009, 5201–5213;
i
For R’ = 1-adamantyl;
j
For earlier papers on dihalodigermenes, see references [5] and [6] cited in Ref. [128];
k
Best described as a germanium/carbon ylide, with the negative charge located at the germanium atom;
l
Indicates the presence of an active lone pair at the germanium atom, and excludes the possibility of a Ge–C (of the three-membered carbocycle) π bonding;
m
The three-membered ring is oriented almost perpendicular to the germole ring;
n
r(K-Ge) = 3.946 Å, r(K-O) = 2.782 Å, r(C-O) = 1.241 Å;
o
r(K-Ge) = 3.855 Å, r(K-O) = 2.730 Å, r(C-O) = 1.236 Å;
p
r(K-Ge) = 3.613 Å, r(K-O) = 2.740 Å, r(C-O) = 1.231 Å;
q
HOMO [π(As = Ge)] – LUMO [π*(As = Ge)];
r
HOMO-1 [n(As), lone pair] – LUMO [π*(As = Ge)];
s
For R = Me;
t
Best described as R2Ge:→Si(0)←:GeR2;
u
v
∠GeSiGe = 80.1°;
For compound 51a.
1.4 Doubly Bonded Compounds
The structures of RR’E=ERR’ (E=Si, Ge, Sn, Pb) compounds were studied and analyzed extensively by both theory and
experiment over the last four decades. These studies were reviewed in many comprehensive reviews [15, 16, 18, 24, 25, 44,
45, 70, 154, 155]. The main structural and bonding aspects of these compounds, which were previously reviewed, are
briefly summarized below. New insights gained more recently regarding the nature of bonding in these doubly bonded
compounds have been added.
The most surprising structural feature of the heavier group 14 alkene analogues, R2E=ER2, which attracted great
attention, is probably their nonplanar structures (Table 1.1) [15, 16, 18, 24, 25, 44, 45, 154, 155], in sharp contrast to the
planar structure of alkenes R2C=CR2. This contrast indicates that simplistic analogy between carbon and its heavier ana-
logues is wrong, and that the heavier group 14 elements have entirely different bonding characteristics. This unexpected
experimental observation was predicted by theory before many of these compounds were synthesized [156, 157], and in
many cases after their synthesis, the experimental bending angles were nicely reproduced by theory [44, 45, 70, 158, 159].
The successful computational predictions in this field that preceded experiments were among the early victories of compu-
tational chemistry, which in the 1970s and 1980s still met considerable scepticism by experimentalists.
1.4.1 Bonding Models

As mentioned above, for many decades the heavier group 14 elements were believed to be reluctant to form π bonds
(classical “double bond rule” [79, 80]). After the first multiply bonded compounds were isolated, new questions of great
theoretical relevance arose. Why, in contrast to carbon, do its heavier analogues form compounds with very different
geometries than the analogous carbon compounds? For example, why are doubly bonded compounds non-planar and
have trans-bent structures? Why are triply bonded compounds bent and not linear? What is the nature of these distorted
π bonds? Are they “real” double bonds? These questions raised a burst of theoretical research accompanied by vibrant
debate in the last four decades [18, 25, 44, 45, 70, 160–164]. Below we review the different views of theory on these
intriguing fundamental questions.
A major fundamental difference between elements of the first (C to F) and higher rows of the Periodic Table is their
most probable valence orbital radii. For carbon, the most probable radius of the 2s orbital is relatively expanded due to
Pauli repulsion from the 1s electrons, while the 2p orbital that is not shielded by an inner p shell is relatively contracted.
This results in very similar radii of the 2s and 2p orbitals. Moving down group 14, the atomic np orbitals are much more
expanded as a consequence of intraatomic Pauli repulsion from orthogonal inner shell (n-1)p orbitals. Consequently, the
radii of the ns and np orbitals (n > 2) diverge significantly
[27]. Δr = rp–rs exhibits a zigzag increase from Si to Pb,
caused by d-block contraction (Ge) and relativistic effects
(Sn, Pb) (Table 1.1 and Figure 1.4). The similar radii of the
s and p valence orbitals of carbon (and other first row ele-
ments) facilitates hybridization. In contrast, for the
heavier main group elements, hybridization is much less
favorable due to the dissimilar radii of their valence ns
and np orbitals. Kutzelnigg introduced the term “hybrid-
ization defects” for this phenomena [27]. The increasing
“hybridization defects” down group 14 have a crucial
effect on the structures and bonding of heavier group 14
compounds [70, 165]. The increase in the trans-bending
angle, and in the planarization energy of the trans-bent
H2E=EH2 (C2h) (Table 1.3) moving down group 14, are
manifestations of increasing “hybridization defects” [27,
42, 115]. Similarly, the much higher inversion barriers of
e.g., PH3 (35.1 (calculated) [166]) vs. NH3 (5.8−6.0 kcal/
mol [166–168] (calculated)) and SiH3- (26 kcal/mol
(MP2/6-31+G(d)) [169] vs. CH3- (2.5 kcal/mol (CCSD(T)/
Figure 1.4 Calculated ns and np orbital radii of maximal
electron density of group 14 elements [27, 37, 115]. Reproduced aug-cc-PVQZ) [169]), was also rationalized by the smaller
with permission from reference [115]. Copyright (2020) American tendency for hybridization of the ns and np orbitals in the
Chemical Society. heavier elements [115, 166]. The decrease in the
1.4 Doubly Bonded Compounds 17
dissociation energy of H2E=EH2 (C2h) to their EH2 fragments (see below, Table 1.3, section 1.4.2) was also rationalized by
the increasing destabilization of heavy alkene analogues, due to the lack of effective iso-valent hybridization and the
enhanced stability of the EH2 fragments [42]. The non bonding lone-pair orbital of EH2 has mainly s orbital character,
thus, lowering its energy, while the E–H bonds are essentially made of non-hybridized p orbitals strengthening the E–H
bonds and stabilizing the divalent hydrides (“inert pair effect”) [42, 165]. Electronegative substituents enhance “hybrid-
ization defects” in heavier p-block elements, thus destabilizing the olefin-like molecules, while their effect on the low-
oxidative states (e.g., ER2) where hybridization is less important, is marginal [42, 165].
The Pauli repulsion, caused by core electrons in heavier group 14 elements, has an important effect on the E–E π and
σ bonds strengths. DFT calculations by Ziegler and Jacobson have shown that the increase in core-core Pauli repulsion
between the E atoms forming the E=E bond (i.e., interactions of the valence orbitals of one E atom with the inner shell
orbitals of the other E atom forming the bond, termed interatomic Pauli repulsion [170, 171] or inner shell repulsion
[79]), weakens the E–E σ bond and increases the interatomic E–E distance, which in turn also lowers the overlap of the
p orbitals weakening the π bond [170, 171]. It is argued that the linear p overlap in the σ bonds is more effective than the
sideway π overlap, making the π bonds more sensitive to changes in the bond distance. In contrast, a study of the varia-
tion of orbital overlap as a function of internuclear distance found that π bonds (not supported by an underlying σ bond)
can be shorter than σ bonds and are not inherently weak [172]. Thus, it is the underlying σ bond that actually determines
the E=E bond strength. Analysis of the nature of bonding in trans-bent HE≡EH (E=Si, Ge, Sn) emphasizes the impor-
tance of the E–E σ bond in stabilizing the trans-bent structures. VB calculations [173, 174] show that the σ-frame prefers
trans-bending and the π bonding opposes this distortion. In HC≡CH, the destabilization of the π bond upon bending
overrides the propensity of the σ-frame to distort, while in the heavier congener molecules, the stabilization of the
σ-frames by trans-bending overcomes the destabilization of the total π bonding and thus results in trans-bent molecules
[173, 174]. The increasing core-core repulsion down the group leads to a significant decrease in the stability of a E=E
double bond as well as of a E–E single bond; thus for E2H4, E=Sn and Pb, the hydrogen dibridged isomer, HE(μ‒H)2EH
becomes more stable than the trans-bent doubly bonded isomer H2E=EH2 and the mono-bridged isomer H2E(μ‒H)EH
[70, 162]. For E2R4 (R=electronegative substituent) “hybridization defects” are enhanced significantly and the dibridged
isomer becomes the global minimum for E=Ge, R=F, Cl, Br. For E=Ge, R=F the dibridged isomer is more stable than
F2Ge=GeF2 by 18.3 kcal/mol (at BP86/def2-TZVpp) [70]. At MP2(FCI)/cc-pwCVTZ(-PP) R2Ge=GeR2, R=F, Cl, Br, I,
were located as transition states [175]. At a variety of other DFT levels, F2Ge=GeF2 dissociates to two GeF2 fragments
upon geometry optimization [176]. See section 1.4.2.2.2.1 for a detailed discussion on the effect of substituents on the
structures and stability of various Ge2R4 isomers. The above discussion focuses on the effect of the inherent difference
in the radial extension of the valence ns and np orbitals on structure and bonding. Other bonding models are discussed
below.
An alternative rationale for the preferred trans-bent geometries of heavy group 14 analogues of alkenes and acetylenes
(R2E=ER2 and RE≡ER, respectively) is arising from second order Jahn-Teller (SOJT) effects [43, 87, 158–161, 171, 177].
The SOJT effects are caused by mixing of occupied π (HOMO) and empty σ* (LUMO+1) molecular orbitals which acquire
the same symmetry (bu) upon trans-bending (Figures 1.5 and 1.6). The mixing of σ and π* orbitals is less important [171].
The extent of orbital interactions and the resulting stabilization of the trans-bent structure is inversely proportional to the
energy difference between the interacting orbitals.
Figure 1.5 A schematic description of the π-σ* mixing (SOJT) upon trans-bending of R2E = ER2.
Figure 1.6 Orbital symmetries and orbital energies of D2h (left) and C2h (right) H2Ge=GeH2. Reprinted with permission from Ref. [159].
Copyright (2020), Royal Society of Chemistry.
The π-σ* energy separation in planar D2h H2E=EH2 decreases upon moving to the heavier elements in group 14; ΔE (eV,
at ωB97X-D/def2-TZVPP) = 14.54 (E=C), 9.78 (E=Si), 9.05 (E=Ge), 7.44 (E=Sn) [159]. As a result, the orbital interaction
lization energies associated with the π → σ* mixing, which increase in the order (in kcal/mol, at B3LYP/def2-TZVPP//
energies and electron delocalization increase going down group 14. This is manifested also in the NBO second order stabi-
CCSD(T)/def2-TZVPP): 3.64 (Si), 8.83 (Ge), 24.41 (Sn) [178], 47.0 (Pb) [179]. Simultaneously, the trans-bending angles
widen [16, 18]. The barriers for planarization (or linearization of heavy acetylene analogues) increase down group 14 [43,
70, 159, 171], thus, For H2E=EH2 they are (in kcal/mol): 0.0 (E=C), 0.9 (E=Si), 2.7 (E=Ge), 10.1 (E=Sn) [159], 23.2 (E=Pb)
[171] (see also Table 1.3), and correlate linearly with the π-σ* energy separation for heavy E-elements (Figure 1.7) [159].
increase in the π(E=E) → σ*(E–E) electron delocalization [178].

The E=E Wiberg bond indices (WBIs) decrease from 2.05 (E=C) to 1.90 (E=Si), 1.79 (E=Ge), 1.54 (E=Sn), reflecting the
Figure 1.7 Planarization (inversion) barriers of H2E=EH2 vs. the π-σ* energy gap (ΔE, eV) for ethylene (D2h, ΔE=14.54) and its heavier
congeners (E=Si (ΔE=9.78), Ge (ΔE=9.05), and Sn (ΔE=7.44)) in C2h symmetry. Reproduced with permission from Ref. [159]. Copyright
(2020) Royal Society of Chemistry.
Another model for understanding the structures of R4E2 compounds is based on the ground state multiplicity of the R2E
fragments and their singlet-triplet energy gap (ΔEST). Carbenes, R2C:, R = alkyl, aryl, are ground state triplets (3B1), while
X2C:, X = electronegative substituents, e.g., halogen, NR2, OR, are ground state singlets [180, 181]. Heavier R2E: are all
ground state singlets (1A1) [182] (Figure 1.8a, Tables 1.3, 1.5 and 1.6). The reasons for this reversal in multiplicity were
analysed [183]. The association of two triplet ER2 (3B1) molecules, forms a planar alkene-like structure (Figure 1.8b). In
contrast, for two singlet ER2 (1A1) molecules to form a planar double bond, they have first to be excited to the triplet state,
paying the cost of the singlet-triplet energy gap (ΔEST); consequently the E=E bond is weakened [184]. Instead, singlet ER2
(1A1) fragments prefer to interact via two donor-acceptor interactions, in which the lone-pair orbital of one ER2 fragment
donates electrons into the empty p orbital of the other ER2 fragment, forming a trans-bent doubly bonded compound
(Figure 1.8c) [70, 160–162]. Based on the trans-bent X-ray structure of the first isolated distannene [(Me3Si)2HC]2
Sn=Sn[CH(SiMe3)2]2, (2), Lappert et al. suggested that 2 results from a donor-acceptor interaction of two singlet SnR2
monomers (Scheme 1.1) [84–87].
Figure 1.8 Bonding models of the interaction of two triplet (3B1) and singlet (1A1) R2E fragments. (a) triplet and singlet R2E;
(b) Interaction of two R2E in the triplet state, forming a planar R2E=ER2; (c) Lone-pair donor-acceptor interaction of two R2E in the
singlet state, forming a trans-bent R2E=ER2; (d) E–X bond-pair donation, forming a dibridged structure; (e) Lone-pair donation
from X forming a dibridged structure.
Descending group 14, the lone-pair orbital of R2E acquires more s-character and is stabilized (“inert pair effect”) and is
less prone to donate electrons to the partner R2E fragment, reducing the tendency to form an E=E bond. At the same time
the E–R bonds become better donors, donating charge into the empty p orbital of the second R2E fragment, thus favoring
dibridged isomers (Figure 1.8d) [70]. Substituents that enhance the “inert pair effect”, e.g., F, prefer dibridged structures
over the doubly bonded isomers for the heavier element compounds [70]. Another explanation for the preference of a
dibridged structure for E2R4 when R are electronegative substituents bearing lone pairs (e.g., F), is the mutual donation of
the substituents’ lone pair into the empty p orbital of the tetrylene (Figure 1.8e) [185, 186].
In a series of important papers, by Carter and Goddard [184] and by Malrieu and Trinquier [160–163, 177], they sug-
gested simple criteria that predict the occurrence of trans-bent E=E double bonds (B), the degree of their trans-bending, as
well as the occurrence of other structural isomers, e.g., a dibridged isomer (C) (Scheme 1.2). These criteria, known as the
“CGMT” criteria, compare ΔEST of the R2E fragments that compose E2R4 with the overall σ+π bond energy (Eσ+π) of
planar R2E=ER2. According to the CGMT approach, for homonuclear R4E2 molecules, a trans-bent doubly bonded struc-
ture (B) is predicted to be more stable than the planar structure (A) or the dibridged (C), when ΔEST of ER2 is in the range
given in Eq. (1.1):
¼ Eσ+π ≤ ∆EST ≤ ½ Eσ+π (1.1)
When ΔEST is smaller than ¼ Eσ+π, a planar doubly bonded species is predicted, while when it is larger than half the
double bond energy a dibridged isomer C is predicted. For E heavier than carbon, the double bond energy (Eσ+π, ΔEdiss)
decreases and ΔEST increases, leading to trans-bent structures with increasing bending angles as E is heavier, or to dibridged
structures (Table 1.3) [70].
1.4.2 Homonuclear Ge=Ge Compounds

1.4.2.1 The Parent H2Ge=GeH2 and Its Isomers: Structures and Potential Energy Surface
As emphasized above, unlike H2C=CH2 which has a planar D2h skeleton (A), calculations show that H2E=EH2
(E=Si-Pb) possess a trans-bent C2h structure B (Table 1.3). The planar structure is a transition state between two iso-
meric trans-bent structures B [44, 45, 70, 158, 159]. Upon moving from carbon to heavier group 14 elements, the
trans-bending angle and the barrier for planarization increases from 31.4° and 0.8 kcal/mol for E=Si to 47.9° and
4.2 kcal/mol for E=Ge, reaching a bending angle θ of 53.2° and a barrier for planarization of ca. 27 kcal/mol for E=Pb
[90] (Table 1.3). A SCF calculated PES of the planarization energy vs. the trans-bending angle (Figure 1.9) shows the
significant increase of the barrier for planarization on moving down group 14 [87]. Simultaneously, the dissociation
energy of H2E=EH2 to two EH2 (1A1) fragments is reduced, i.e., ΔEdiss is (at 0 K, in kcal/mol, at BP86/def2-TZVPP
[70]): 178.8 (E=C, dissociation to two triplet CH2 fragments); 67.8 (E=Si); 51.3 (E=Ge); 28.9 (E=Sn, at LDA/TZ+p)
[171]; and 10 (E=Pb, at LDA/TZ+p) [171], indicating that actually H2Pb=PbH2 dissociates at room temperature
(Table 1.3).
The calculated Ge=Ge bond length in H2Ge=GeH2 is 2.275–2.346 Å (depending on the computational level,
Figure 1.10, Table 1.3), shorter than that of a Ge–Ge single bond length of 2.40–2.46 Å (exp. r(Ge-Ge) = 2.403 Å [187])
in H3Ge-GeH3 [188]. The calculated trans-bending angle is ca. 42–47° [43–45, 70, 188, 189]. The trans-bending angle
in H2Ge=GeH2 is significantly larger than in H2Si=SiH2 (e.g., θ = 31.4°). The experimental Ge=Ge bond lengths and
the trans-bending angles in isolated digermenes, R2Ge=GeR2 (R are bulky alkyl and aryl ligands), span over a large
range of 2.2–2.49 Å [15, 18, 24] (Figure 1.11a) and of ca. 15–45° [18] (Σ∠Ge = 327–358°), respectively [15, 18, 24]. The
bond distances in 60% of the isolated digermenes (Figure 1.11a) are in the range of those calculated for H2Ge=GeH2
(Figure 1.10).
As discussed above, several additional structural isomers, C–F (Scheme 1.2), were located by calculations as minima on
the E2H4 (E=C–Pb) potential energy surface (PES). The calculated relative energies of isomers B, C and F and the struc-
tural parameters of isomer B are presented in Table 1.3. The geometrical parameters of isomers B-F for E=Ge, R=H are
presented in Figure 1.10. The most stable isomer for E=Si and Ge is the doubly bonded trans-bent isomer B, but for E=Sn
and Pb, the most stable isomer is the trans-dibridged isomer C (Table 1.3) [44, 45, 70, 160–162]. The hydrogen-singly
bridged isomer E is a minimum on the PES for E=Ge [189], Sn, and Pb [162, 163]. For Sn2H4 and Pb2H4 the calculated sta-
bility order of the isomers is: C > E > F > B, i.e., the doubly bonded isomer B is the least stable isomer [163].
The PES of Ge2H4 is relatively flat and spans over a range of ca. 14 kcal/mol compared to the PES of Si2H4 that spans over
a range of 22 kcal/mol (Table 1.3) [70, 188, 189, 194].
H2Ge=GeH2 and HGe-GeH3 are nearly degenerate, with H2Ge=GeH2 being slightly favored (at most by ca. 3 kcal/mol,
depending on the level of calculation, Tables 1.3 and 1.4) [70, 188, 189, 194]. The calculated barrier for the isomerization of
Table 1.3 Calculated geometric parameters and relative energies of isomers B, C and F (ΔE) on the PES of E2H4 (E=Si, Ge, Sn, Pb), the
dissociation energy of B to EH2 fragments (ΔEdiss) and the singlet-triplet energy gaps (ΔEST) of the corresponding fragments.a,b
H2E=EH2 (B) HE(μ-H)2EH (C) HEEH3(F, 1A’) EH2
E r(E=E) θ ΔEc ΔEdissd ΔEe ΔEdissf ΔE ΔESTg

h h i j
C 1.322 180 (0.0) 178.7 164.7 27.3 72.3 ;79.1 −15.8;
−9.03k;
−(8.99l)
Si 2.178 31.4 0.0 (0.8) 67.8 [100.0] 18.7 31.2h 7.9m 16.5; 19.6n;
(21.0o)
Ge 2.300 47.9 0.0 (4.2) 51.3 [93.7] 6.8 26.9h 3.4p 23.3
q h j
Sn 2.175 50.6 0.0 (11.5) 28.9 [74.4] −9.4; 40.5; 33.2 −2.1 27.3
−9.1j
Pb 2.922 53.2 0.0 (27.3) 10.0q [60.4] −21.8; 38.5; 28.7h −16.4 j 35.5
−23.9 j
a
Bond lengths in Å, bond angles in degrees. Energies in kcal/mol;
b
From Ref. [70], at BP86/def2-TZVPP, unless stated otherwise. For other calculated values see Refs. [43–45, 162, 171, 178];
Dissociation energies: H2E=EH2 (C2h) → 2H2E: (1A1). In brackets, ΔEdiss of H2E=EH2 (planar, D2h) → 2H2E: (3B1);
c
In parenthesis, the relative energy of the planar doubly bonded isomer A;
d
e
Energy difference between isomers C and B;
f
Dissociation of C to 2H2E: (1A1);
g
Experimental values in parenthesis;
h
From Ref. [162], at CI//HF/DZ;
i
From Ref. [190];
j
From Ref. [162] at CI/DZP;
k
At CASSCF-SOCI with the TZ3P(2f,2d)+2diff basis set [191];
l
See references cited in Ref. [191];
m
At the G1 level, from Ref. [190];
n
At MRSOCI [192];
o
From Ref. [193];
p
At CCSD(T)/aug-cc-pVTZ//B3LYP/6-311G(d,p) [189], see Table 1.6 for values at other computational levels;
q
At LDA/TZ+P with nonlocal corrections [171].
Scheme 1.2 Possible isomers on the R4E2 potential energy surface.
and barriers were calculated for the isomerization of H2Ge=SiH2 → HGeSiH3. The isomerization energy of H2Ge=SiH2 →
H2Ge=GeH2 to HGeGeH3 at several CCSD levels of theory is 12.9–14.0 kcal/mol (Table 1.4) [195]. Similar reaction energies
HSiGeH3 is significantly higher than the isomerization of H2Ge=SiH2 → HGeSiH3. In part, this results from the different
bond strength of the Si–H and Ge–H bonds in H2Ge=SiH2 and in the corresponding products HGeSiH3 or HSiGeH3. The
Figure 1.9 Variation of energy (kJ/mol) with

the trans-bending angle of H2E=EH2 calculated
at the SCF level. The curves for C2H4 and Si2H4
40 C2H Si H were calculated for non-adiabatic bending (i.e.,
4 2 4
with constant values for E–E, E–H bond
distances and H–E–H bond angles). The curves
–1
∆ESCF/KJ MOL
for Ge2H4 and Sn2H4 were calculated for
30
adiabatic bending (i.e., with re-optimized values
for the E–E bond distances and H–E–H angles).
Adapted with permission from Ref. [87].
20 Copyright (1986) Royal Chemical Society.
10
–60 –40 –20 20 40 60

Ge H θ/˚
2 4
–10
–20
–30 Sn H
2 4
(a) 1.545 107.8 (b) 109.1

2.275 108.6
2.305
2.278 107.5
2.310 107.5
H 106.4
115.6 2.311 H
2.346
B Ge Ge 1.537
Ge2H4 1Ag 1.540
H
116.7 1.548
H
116.0 1.556
115.4 1.569
115.1
114.5
1.596
104.9
1.764 91.8 1.589 Neutral (C2h 1Ag)
105.6
75.1
87.7 1.771 74.4 1.534
C D 1.539 113.3
1.545 114.1
Ge2H4 1Ag Ge2H4 1A1
H 1.553 113.8 2.510
1.536 1.557 114.6 2.500
1.543 114.3 2.528
1.548 2.521
1.557 2.554
1.561 Ge Ge
113.8 1.543 1.583
H 110.5 89.7
1.929 1.710 1.593
2.528 107.4 H 88.6
110.5 1.600
128.2 89.0
1.595 86.7 1.546 106.8 110.8 1.612
107.0 106.8 110.9 88.1 H
89.0 110.9 1.617
2.412 1.548 1.598 106.1 111.2 88.7
106.7 106.1
E F
Ge2H4 1A
Ge2H4 1A' Neutral (Cs 1A')
Figure 1.10 (a) B3LYP/6-311G(d,p) optimized structures of isomers located on the G2H4 PES. Adapted with permission from Ref.
[189]. Copyright (2006) Elsevier B.V., and (b) Optimized structures of trans-bent H2Ge=GeH2 and of germylgermylene, at a variety of
DFT levels. Bond lengths in Å and bond angles in degrees. Adapted with permission from Ref. [188]. Copyright (2002) Wiley Periodicals.
(a) (b)
Distribution of Ge=Ge bond lengths in digermenes Distribution of Si=Si bond lengths in disilenes
2.26–2.28 Å >2.28 Å
>2.50 Å 2.20 –2.29 Å 2.23–2.25 Å 3% 1%
4% 14% 8%
2.40–2.49 Å 2.14–2.16 Å
23% 2.20–2.25 Å 34%
22%
2.30 –2.39 Å 2.17–2.19 Å
59% 32%
Figure 1.11 Distribution of (a) Ge=Ge bond lengths and (b) Si=Si bond lengths in experimentally isolated digermenes and disilenes.
Reprinted with permission from Ref. [25]. Copyright (2013) Elsevier.
H2E=E’H2 → HEE’H3 isomerization (E and E’=Ge, Si and C).a

Table 1.4 Calculated reaction energies (ΔE) and reaction barriers (ΔE#) for the
Reaction ΔE ΔE#
H2C=CH2 → HCCH3 74.9b 75.0b

H2Si=SiH2 → HSiSiH3 7.9c 17.3d
H2Ge=GeH2 → HGeGeH3 2.3 to −2.3 12.9–14.0
H2Ge=SiH2 → HGeSiH3 −3.2 to −7.0; −3.6e, −4.8f, −6.3 g 14.4 to 15.7; 11.8e
H2Ge=SiH2 → HSiGeH3 14.1f; 9.4g –
a
In kcal/mol, at various CISD and CCSD levels. From Ref. [195] unless stated otherwise.
For more data, see the citations in previous reviews [44, 45];
b
At MP4/6-311G(d,p) [197];
c
At the G1 level [198];
d
MP3/6-31G(d) [199];
e
At CCSD(T)/6-311(d,p)//B3LYP/6-311G(d,p), from Ref. [200];
f
At CCSD(T)/cc-pVTZ (H, Si) and CCSD(T)/cc-pVTZ-pp (Ge), from Ref. [201];
g
At CISD+Q, from Ref. [196].
Si–H and Ge–H bond strength in H2Ge=SiH2 are 68.5 kcal/mol vs. 57.4 kcal/mol, respectively; in HGeSiH3 the Si–H bond
strength is 90.6 kcal/mol, and the Ge–H bond strength in HSiGeH3 is 84.0 kcal/mol [196]. The contrast with the extremely
high barriers (75 kcal/mol) for the H2C=CH2 to HCCH3 isomerization demonstrates again that analogy between C and its
heavier analogues is misleading.
For Sn2R4, of the four isomers B, C, D and F, a trans-dibridged tin derivative Ar’Sn(μ-H)2SnAr’ (Ar’ = (H3C6-2,6-(C6H2-
2,4,6-iPr3)2) [202] and a dihydrido stannylene derivative Ar”SnSnH2Ar” (Ar” = C6H-2,6-(C6H2-2,4,6-iPr3)2-3,5-iPr2) [203]
were isolated and characterized by X-ray crystallography. Calculations for Ar2H2Sn2 show that stannylene isomer F
becomes more favorable than the dibridged isomer C as the size of the Ar ligand increases [204].
The elusive H 2Ge=GeH2 was isolated and characterized spectroscopically only as a donor-acceptor complex, via
LB1(or LB2)→H2Ge=GeH2→LA, (52, 53), LB1=N-heterocyclic carbene, LB2=nucleophilic N-heterocyclic olefin,

coordination with a Lewis base (LB)/Lewis acid (LA) combination, which stabilize the reactive digermene, i.e.,
digermene, LB2→Cl 2Ge=GeCl2→LA (54) [205] (Figure 1.12), and mixed E=E’ molecules, LB1→H 2Si=EH2→LA,
LA=W(CO)5 (Scheme 1.3 and Figure 1.12) [205]. A similar strategy was used to synthesize and isolate tetrachloro-
E=Ge, Sn [206].
Scheme 1.3 (a) Possible resonance structures of H2Ge=GeH2 and (b) Stable digermene Lewis acid/Lewis base complex.
Figure 1.12 X-ray molecular structures of LB1→H2Ge=GeH2→W(CO)5 (52) and LB2→Cl2Ge=GeCl2→W(CO)5 (54). Reproduced with
permission from Ref. [205]. Copyright (2013) American Chemical Society.
The Ge–Ge bond length in 52 is 2.421 Å which is in the range of a Ge–Ge single bond (see above). Calculations at
M06-2X/cc-pVTZ of model systems of 52 and 53 where the bulky 2,6-iPr2-C6H3 substituent at N was replaced by a Me
group, designated 52Me and 53Me, predict a polar Ge–Ge linkage with 60% of the charge density residing on the W atom
bonded to Ge, due to electron withdrawing by the carbonyl groups. The Wiberg bond index (WBI) of the Ge–Ge bond is
0.87 and 0.91 in 52Me and 53Me, respectively. Comparison with the Ge–Ge WBI of H3Ge-GeH3 of 0.97 and that of H2Ge=GeH2
of 1.79 supports a single covalent bond in 52 and 53, and the bonding mode shown in Scheme 1.3(b). Similar to 52 and 53,
also the parent H2Si-GeH2 and H2Si-SnH2 were isolated as complexes with W(CO)5 and NHC ligands [206]. WBIs calcu-
lated at B3LYP/cc-pVDZ-pp are 0.88 for the Si–Ge bond and 0.79 for the Si–Sn bond, supporting the bonding shown in
Scheme 1.3(b) also for these compounds [206].
Digermene, H2Ge=GeH2 (X1Ag), and germylene HGeGeH3 (X1A’) and their fully deuterated isotopomers were observed by
IR spectroscopy in GeH4 and GeD4 matrices at 12 K, upon irradiation of the matrices with energetic electrons. The digermene
and D4-digermene were identified by their absorptions at 845 cm−1 (ν11), and at 1476 cm−1 (ν5), attributed by calculations to
a GeH2 scissor vibration, and to the GeH2 asymmetric stretching vibration, respectively [189]. Calculations predict also two
stronger bands at 2125 cm−1 (ν5, GeH2 asymmetric stretching) and at 2093 cm−1 (ν10, GeH2 symmetric stretching). The slightly
less stable HGe-GeH3 (F) and its deuterated derivative were also identified by their absorption at 787 cm−1 and 558 cm−1(ν5,
GeH3/GeD3 umbrella), respectively. The vibrational frequencies and IR intensities of H4Ge2 isomers B-F were calculated at
B3LYP/6-311G(d,p) aiding in identifying the experimentally observed species [189]. Tetra-methyl digermene was detected in
nitrogen and argon matrices at 5 K and were identified by Raman and IR spectroscopy [207, 208].
H-migration from the sterically hindered dihydrodigermene Ar’HGe=GeHAr’ (Ar’ = C6H3-2,6-(2,6-iPr2C6H3)2), 55
occurs (Eq. 1.2) in the presence of PMe3, producing a base-stabilized germylene, Ar’Ge-GeH2Ar’, 56 [209]. The experi-
mental X-ray structure of 55 exhibits a trans-bending angle of 20.5° and a Ge–Ge bond length of 2.372 Å [209], longer than
the calculated values for H2Ge=GeH2 of 2.275–2.346 Å [188] (see also Table 1.3 and Figure 1.10), and it is in the upper limit
of the measured bond lengths in isolated Ge=Ge compounds, of 2.20–2.45 Å (Figure 1.11) [15, 18, 24, 25]. The Ge–Ge bond
length in germylene 56 is 2.530 Å, similar to the calculated Ge–Ge bond distance in HGe–GeH3 (Figure 1.10), and the C–
Ge–Ge bond angle is 101.6° being larger than calculated for HGeGeH3 of 89° (Figure 1.10) [209]. Other examples of stable
germylgermylenes are limited, e.g., (2,6-Mes2H3C6)GeGetBu3, an analogous germyl stannylene was isolated as well [210].
PMe3
Ar' Ar' H
toluene H
H (1.2)
Ge Ge + PMe3 Ge Ge
H
Ar' Ar'
55 56
1.4.2.2 Substituent Effects

1.4.2.2.1 Correlation between Structures, Bond Dissociation Energies and ΔEST
In agreement with the CGMT approach, Karni and Apeloig [211] found a linear correlation between ΔEST of HRSi (R=Li, BeH,
BH2, SiH3, F, OH, NH2) and the trans-bending angles at the Si atoms in HRSi=SiH2 and its dissociation energy. Electronegative
and π-donor substituents, F, OH, and NH2, increase ΔEST of the silylene fragments, and consequently, increase the trans-bending
angle and reduce dramatically the dissociation energy of disilene to its fragments [211] and the energy difference between the disi-
lenes and their dibridged isomers C (Scheme 1.2) [185]. At MP2/6-31G(d), the dibridged structure HSi(μ-H)2SiH (C) is less stable
than H2Si=SiH2 (B) by 25.8 kcal/mol (18.7 kcal/mol at BP86/def2-TZVPP, Table 1.3), while the fluorine substituted dibridged
isomers FSi(μ-H)2SiF and HSi(μ-F)2SiH are by only 6.1 and 9.5 kcal/mol, respectively, less stable than HFSi=SiHF [185]. Trinquier
predicted computationally that F2Si=SiF2 isomerizes without a barrier to the dibridged isomer FSi(μ-F)2SiF [161].
Chen and coworkers [212] studied computationally the structures and bond dissociation energies of R2Ge=GeH2,
R2Ge=SiH2 and H2Ge=SiR2 (R=H, CH3, NH2, OH, F, Cl) and also found a good linear correlation between ΔEST of GeR2 or
SiR2, the trans-bending angles and the E=E’ bond dissociation energies. The data in Table 1.5 predicts that for electronegative
π-donating substituents, for which ΔEST of GeR2 is significantly larger than that of GeH2, the energy required to planarize the
trans-bent R2Ge=GeH2 increases significantly. Simultaneously, the Ge–Ge bond length elongates from 2.307 Å (R=H) to
2.483 Å (R=NH2), being longer than the single bond length in H3Ge–GeH3 of 2.40–2.46 Å [188] (exp. r(Ge–Ge) = 2.403 Å
[187]). The trans-bending angle at the Ge atom bearing the substituents (θR) is smaller than in H2Ge=GeH2, but for electro-
negative π-donating substituents, θH is very large, 78–94°. The long Ge=Ge bonds that are in the range of a Ge–Ge single bond
length, the large trans-bending angle θH of nearly 90°, and the significantly smaller BDE for R2Ge=GeH2, R=NH2, OH, F and
better described as R2Ge → GeH2 adducts, where the σ-lone pair of GeR2 donates electrons into the empty p orbital on GeH2,
Cl, relative to R=H, indicate a weak Ge–Ge bond. In our view, these geometric parameters indicate that these compounds are
(57, E=Ge) while the back-donation from GeH2 is small, in contrast to a classical donor-acceptor complex (Figure 1.8c),
leading to a trans-bent double bond. Similar geometry patterns are observed in a variety of NHC-stabilized divalent group 14
adducts [213–215], e.g., NHC→SiCl2 [215, 216], NHC→GeMes2 [216, 217], and NHC→GeI2 [218]. In these adducts the NHC
carbene is nearly perpendicular to the plane of the ER2 unit and the C–E bond is longer than a C–E single bond. In NHC→
GeI2, r(C–Ge) = 2.102 Å [218] vs. 1.969 Å [219] in H3C–GeH3 and 1.784 Å in H2Ge=CH2 [220]. NBO calculations [213] of the
resides mainly (91%) on the Si atom. The calculated extent of σ-donation in NHC→SiH2 is 0.557 electrons and the SiH2→NHC
NHC→SiH2 adduct suggests a Lewis structure having a C–Si polarized σ bond and a localized p(π) lone pair orbital which
back-donation is only 0.170 electrons (calculated using charge delocalization analysis (CDA) [221]). These are all indications
of a donor adduct rather than a doubly bonded compound [213].
E E
57
Table 1.5 Calculated singlet-triplet energy gaps (ΔEST) of R2Ge, relative energies (ΔE) of trans-bent
R2Ge=GeH2 (B) and planar (A) structures, the Ge–Ge bond dissociation energy (BDE) and geometric
parameters of R2Ge=GeH2, R=H, CH3, NH2, OH, F, Cl.a
R H CH3 NH2 OH F Cl
ΔEST 27.5 31.5 59.2 72.3 83.5 63.6

ΔEb −4.83 −6.1 −24.5 −22.6 −26.0 −20.2
c
BDE −52.2 −50.1 −35.9 −29.1 −23.4 −33.5
r(Ge-Ge) (planar, A) 2.224 2.230 2.234 2.232 2.225 2.228
r(Ge-Ge) (trans-bent, B) 2.307 2.337 2.483 2.475 2.467 2.440
θRd 43.45 30.14 12.79 17.61 28.1786.03 32.31
θHe 43.72 59.55 94.64 92.94 78.09
a
Calculated at B3LYP/6-311G(d). Energies in kcal/mol, bond length in Å, angles in degrees. From Ref. [212];
b
Negative values indicate that B is more stable than A. A is not a minimum on the PES;
c
BDE is the difference between the energy of R2Ge=GeH2 and the sum of the energies of GeH2 and GeR2 in
their singlet state. The values given in Table 1.5 were derived from the reported correlation of BDE vs. ΔEST: i.e.,
BDE = 0.515 ΔEST −66.37 (r2 = 0.956) [212]. The individual BDEs calculated directly were not provided;
d
The trans-bending angle at the Ge bonded to R;
e
The trans-bending angle at the Ge bonded to H.
1.4.2.2.2 Substituent Effects on Structures and Isomeric Forms of Ge2R2R’2 Compounds

1.4.2.2.2.1 Electronegative Substituents
1.4.2.2.2.1.1 Halide Substituents
Electronegative substituents significantly stabilize the singlet state of ER2, increasing ΔEST (e.g., Table 1.6, E=Ge). The
large increase in ΔEST from 16.5, 23.3, and 27.3 kcal/mol for EH2 (E=Si, Ge, Sn, respectively), to 69.7, 81.5, and 80.2 kcal/
mol, for EF2 (E=Si, Ge, Sn, respectively), leads to a significant stabilization of the dibridged isomer C [70, 176, 222] and it
is the most stable E2X4 isomer. The trans-bent isomer B of F2Ge=GeF2 is not a minimum on the potential energy surface
[175, 176, 222]. The dibridged Ge2F4 isomer, C, was identified and characterized in matrix by IR and Raman spectroscopy
[164].
Hargittai and coworkers studied computationally the PES of E2R4 (E=Si, Ge, Sn, Pb; R=F, Cl, Br, I) using the
MP2(FCI)/cc-pwCVTZ(-PP) level of theory [175]. The trans-dibridged isomer, C, is the global minimum for all com-
pounds, and it is only slightly more stable than the cis-dibridged isomer. The germylgermylene divalent isomer F is
higher in energy by ca. 30 kcal/mol for R=F, but it becomes relatively more stable for R=Cl, Br, and I (Table 1.6).
Structural and NBO analysis of the bonding in R3Ge–GeR for R=Br, Cl, and I, reveals that these are better described as
mono-bridged isomers E. For example, in R3Ge–GeR, R=Br, Cl, and I (see atom numbering in Table 1.6), r(Ge3–R4) of
2.443, 2.596, and 2.788 Å, respectively, having Wiberg bond indices (WBIs) of 0.43, 0.46, and 0.52, respectively, are
nearly identical to r(Ge1–R4) of 2.389. 2.525, and 2.711 Å and WBIs of 0.47, 0.52, and 0.58, respectively. Meanwhile,
Ge1–R6 and Ge3–R5 bonds (in F), are significantly shorter, e.g., for R=Br, they are 2.284 and 2.323 Å, respectively, and
for both the WBIs are 0.84 [175].
ΔEST for GeHR (R=F, Cl, Br, I) is significantly smaller than for GeR2 (Table 1.6), and according to the CGMT model the
relative stability order of the isomers on the PES of (GeHR)2 is expected to be different than that of the (GeR2)2 PES. The
relative energies calculated for the isomers of E2Me2Br2 shown in Figure 1.13 (the isomeric notations in this paragraph are
as in Figure 1.13) show that for E=Si, (E)-dibromodimetallene (A) is the most stable isomer. The corresponding silylsi-
lylene (E) has almost the same energy [186]. The bulkier substituted Bbt(Br)Si=Si(Br)Bbt (Bbt = 2,6-[CH(SiMe3)2]-4-
[C(SiMe3)3]-C6H2)) is more stable than its isomer E, by 14 kcal/mol [186]. Similarily, dihydrodisilene Bbt(H)Si=Si(H)Bbt
is more stable than the corresponding silylsilylene E by 13.2 kcal/mol, and the barrier for the isomerization of Bbt(H)
Si=Si(H)Bbt to Bbt(H2)Si-SiBbt is 19.6 kcal/mol (at B3PW91/6-311+G(2df)[Si]:6-31G(d)). Bbt(H2)Si-SiBbt was suggested as
an intermediate in the slow decomposition of Bbt(H)Si=Si(H)Bbt at 80° [186]. The dibridged isomers (C, D) are signifi-
cantly less stable for E=Si.
For E2Me2Br2, E=Ge, germylgermylene E is the most stable isomer. The doubly bonded isomer A is 5 kcal/mol higher in
energy. The dibridged isomers C and D are only slightly less stable than the doubly bonded isomer A. For E=Sn, both
dibridged isomers are significantly more stable than the doubly bonded isomer A (Figure 1.13) [186] as also predicted for
Table 1.6 Relative energies (kcal/mol) of isomers B-F on the Ge2R4 (R=H, F, Cl, Br, I) PES.
Isomer B C D E F
R θ R R R5 R5
R Ge Ge Ge1 Ge3
Ge Ge R
R R R4 R2
Ge Ge Ge1 Ge3
R R R R6
R R2
R R R6 R4 GeR2 ΔEST GeHR ΔEST
H 0.0 11.5a, 6.9b, 9.0c, 6.8d 13.6a, 8.6b, 11.6c 4.8a, 1.9b 3.4a, −0.24b, 2.4c; 2.8e 23.3f, 26.7g −
h i g i g
F - 0.0 1.8 , 1.7 - 26.6 , 29.4 85.0 46.2g
i i g,j
Cl - 0.0 1.4 - 10.4 64.1 42.0g,j
Br - 0.0 1.9i - 8.1i 57.2g,j 40.3g,j
i i k,l
I - 0.0 2.7 - 4.6 47.7 37.5k,l
a
At CCSD(T)/aug-cc-pVTZ//B3LYP/6-311G(d,p), from Ref. [189];
b
At B3LYP/6-311G(d,p), from Ref. [189];
c
At CI/DZP from Ref. [162];
d
At BP86/def2-TZVPP from Ref. [70];
e
At BP86/DZP++ from Ref. [188];
f
From Ref. [70], at BP86/def2-TZVPP;
g
At B3LYP/DZP++, from Ref. [223];
h
At BP86/DZP++, from Ref. [176];
i
At MP2(FCI)/cc-pwCVTZ(-PP) from Ref. [175];
j
For values at other computational levels see Refs. [44, 45, 224];
k
At B3LYP/6-311g(d,p), from Ref. [223].
Figure 1.13 Calculated relative energies (kcal/mol) of E2Me2Br2 isomers at B3PW91/6-311G(3d), [TZ(2d) for Sn, and 6-31G(d) for C
and H]. Energies of E-1,2-dibromo-1,2-dimethyldimetallene are set to zero). Negative relative energies indicate more stable species.
Reproduced with permission from Ref. [186] Copyright (2013) Chemical Society of Japan.
Sn2H2 (Table 1.3) [162]. In fact, all known donor-free dimeric hydridostannylenes, (RHSn)2, adopt the trans-dihydrogen-
bridged structure RSn(μ-H)2SnR (e.g., R = 2,6-Dip2-C6H3, Dip = 2,6-iPr2-C6H3) [203, 225] or stannystannylene structure,
RSnSnH2R (R = 2,6-Tip2-C6H-3,5-iPr2 (Tip = 2,4,6-iPr3-C6H2)) [203, 225], and not the alkene-like structure [226]. It is
interesting to note that for E2Me2Br2, the Ge compounds differ from those of their closest neigbours, Si and Sn, both qual-
itatively (in their most stable isomer) and quantitatively (the PES is flatter for Ge than for Si or Sn (excluding isomer E)).
The calculated dissociation energies (ΔEdiss) of Me(Br)E=E(Br)Me to two E(Br)Me fragments decrease as E is heavier.
ΔEdiss (in kcal/mol, at B3PW91/6-311G(3d), [TZ(2d) for tin, and 6-31G(d) for C and H]) are: 37.5 (E=Si) > 23.1 (E=Ge) > 14.6
(E=Sn)[186]. These calculated dissociation trends are in agreement with experimental results that in solution dibromodisi-
lene is stable, dibromodigermene is in equilibrium with its bromogermylene fragments [129], while for E=Sn only the
Br-bridged isomer is observed [186].
Bbt(Br)Ge=Ge(Br)Bbt (25, Table 1.2) was isolated as stable orange crystals at −78°C. [129, 186] Its Ge=Ge bond length is
2.509 Å, longer than other known Ge=Ge bond length of 2.21–2.44 Å [18], and even longer than the Ge–Ge single bond of
2.463 Å in (GePh2)6 [87]. The trans-bending angle at Ge is 44.6°, more pyramidal than in other digermenes which are in the
range of ca. 10–40° [18], but no twist of the double bond was observed [129]. The calculated (B3LYP/6-31+G(d)) r(Ge=Ge)
and trans-bending angle in H(Br)Ge=Ge(Br)H are 2.378 Å and 53.2°, respectively, and 2.414 Å and 48.1°, respectively, in the
more bulky substituted Mes(Br)Ge=Ge(Br)Mes [129]. These calculations indicate that the Ge=Ge bond in 25 is elongated due
to the steric repulsion between the bulkier Bbt substituents. However, the trans-bending depends on an intrinsic property of
the GeRBr germylene, e.g., its ΔEST (see above). In toluene solution, 25 is in equilibrium with its germylene fragments [129].
The synthesis and X-ray crystallography characterization of additional 1,2-dihalodigermenes, (E)–Ar(Cl)
Ge=Ge(Cl)Ar, Ar = 2,6-Mes2-C6H3 [227, 228] (Mes = 2,4,6-Me3-C6H2)) (58); Ar = 2,6-Tip2-C6H3 (Tip = 2,4,6-iPr3-
C6H2) (59) [227], were reported by Power’s group. Very recently, Matsuo’s group reported the synthesis of (E)–
Eind(R)Ge=Ge(R)Eind, R=Cl (24b) and Br (24a) (for the definition of Eind, see Table 1.2) [128]. The Ge=Ge bond
length in 58, 59, 24b, and 24a are 2.443, 2.363, 2.412, and 2.414 Å, respectively, and the trans-bending angles are
39.0, 36.8, 44.3, and 43.3°, respectively. Twisting about the double bond was not observed [128]. Based on UV-Vis
spectroscopy, it was concluded that in solution 24a dissociates to its germylene fragments, and 25 is in equilibrium
with the GeBrBbt fragments. The different behavior of 24a and 25 was explained by dispersion effects. The computed
dissociation energy (ΔG) of the Ge=Ge bond in 24a (at B3PW91-D3/6-311G(3d,f) (Ge, Br) and 6-311G(d) (H, C, Si),
including dispersion) is 7.8 kcal/mol, compared to 15.3 kcal/mol in 25. Compound 24a can be regenerated from the
germylenes by removal of the solvent [128].
ΔEST of Ge(SiH3)X, X=F, Cl, Br, are (at B3LYP/DZP++): 31.1, 28.6, and 27.7 kcal/mol, respectively, significantly smaller
than those of Ge(CH3)X, X=F, Cl, Br, of 48.0, 43.5, and 41.7 kcal/mol, respectively (at B3LYP/DZP++), as expected for SiH3
vs. CH3 substituents [223]. Based on the CGMT model, we predict that their doubly bonded dimers e.g., X(SiR3)Ge=Ge(SiR3)X,
X=F, Cl, Br, may be less pyramidal at the Ge atoms and with shorter and stronger Ge=Ge bonds, compared to the large
trans-bending angles and long Ge=Ge bonds found in X(Ar)Ge=Ge(Ar)X (e.g., compounds 24a, 24b, 25, (Table 1.2) and 58,
59). Computational studies are required to assess this prediction.
1.4.2.2.2.1.2 Amino substituents

Calculations and experimental evidence have shown that diamino-tetrylenes (E(NR2)2) do not dimerize to form tetraamino-
E=E molecules, in line with their large ΔEST values, e.g., ΔEST = 79.3 kcal/mol for Si(NH2)2 [229]. Calculations predict that
(H2N)2Si=Si(NH2)2 is not a minimum on the PES, and that the dibridged H2NSi(μ-H2N)2SiNH2 should be observed [229,
230]. Following these calculations Kira and coworkers in an elegant experiment have confirmed the existence of the
dibridged iPr2NSi(μ-iPr2N)2SiNiPr2 [231].
A similar behavior is found for amino substituted germanium and tin compounds. Reaction of ArECl (E=Ge, Sn, Pb) in
liquid ammonia produced trans-dibridged ArE(μ-NH2)2EAr (E=Ge, Ar = Ar′ = 2,6-iPr2-C6H3 or Ar = Ar* = 2,6-(2,4,6-iPr3-
C6H2)2-C6H3; E=Sn, Ar=Ar*; E=Pb, Ar=Ar*) that were characterized spectroscopically [232].
E(N(SiMe3)2)2, E=Ge, Sn, are monomeric in the solid state and do not dimerize in solution [87]. Calculations at B3PW91
reveal that the Ge–Ge bond length in (Ge(N(SiMe3)2)2 is 5.841 Å, more than twice the van der Waals radius of a Ge atom
longer than a Ge–Ge single bond [117]. The calculated dissociation (ΔH) energy of ((Me3Si)2N)2Ge=Ge(N(SiMe3)2)2 → 2
(2.11 Å [233]) and it is contracted to 3.798 Å at B3PW91-D3 when attractive dispersion forces are included, still significantly
Ge(N(SiMe3)2)2 is −7.0 kcal/mol (i.e., exothermic) at B3PW91, but increases to 3.6 kcal/mol when dispersion forces are
included. However, ΔG for dissociation (at 25°C and 1 atm.) is −12.2 kcal/mol (i.e., exergonic), indicating that monomeric
species are favored under these conditions [117].
Additional experimental support for the conclusion that diaminosilylenes avoid dimerization to tetraamino-disilenes
was reported by West, Apeloig, and coworkers [234], who showed that the stable N-heterocyclic silylene 60, R=tBu, does
not dimerize to form disilene 61, E=E’=Si (Scheme 1.4). Instead, silylene 62, E=E’=Si, substituted by one amino group and
a silyl group is formed as an intermediate, and it dimerizes to Z-diaminodisilyldisilene, 63, E=E’=Si, R=tBu, which is sta-
bilized by two silyl groups. Calculations at B3LYP/6-31G(d) found that 63, E=E’=Si, R=Me is a minimum on the PES while
the tetraaminodisilene 61, E=E’=Si, R=Me, is not. 63, E=E’=Si, R=tBu, exhibits a very long Si=Si bond of 2.289 Å (2.285 Å
calc. for R=Me), an extremely large trans-bending angle of ca. 33° and a Si–Si–N twist angle of 25°. The formation of 63 and
not of 61 is consistent with the much larger ΔEST of (Me2N)2Si of 68.7 kcal/mol relative to that of H3Si(Me2N)Si of 45.2 kcal/
mol (B3LYP/6-311G(d,p) [234].
Scheme 1.4 Dimerization of N-Heterocyclic tetrylenes

Similarly, a reaction of silylene 60, E=Si, R=tBu, with germylene 60’, E’=Ge, R=tBu, did not produce the tetraamino-
substituted germasilene 61, E=Si, E’=Ge, but instead yielded digermene 63, E=Ge, E’=Si (Scheme 1.4) substituted by two
amino groups and two stabilizing silyl groups [235, 236]. In 63, E=Ge, E’=Si, R=tBu, r(Ge-Ge) is 2.45 Å [235, 236], longer
than in alkyl and aryl substituted digermenes. The trans-bending angle is ca. 41° and the twist angle is 22°. Reaction of
silylene 60 with Sn[N(SiMe3)2]2 yields, as a final product, the hydridodisilylstannane, 64 [235]. Calculations to study this
interesting reaction are welcomed.
(E)-(R2N)HGe=GeH(NR2) (22 [126], 23 [127], Table 1.2) were synthesized by hydrogenation of amido-digemynes 65 and
67, respectively (Scheme 1.5a and 1.5b respectively), and were characterized by X-ray crystalography [126, 127]. A UV-Vis
spectroscopic experiment led to the conclusion that digermene 22 is in equilibrium with germylene 66, which was trapped
by DMAP (4-dimethylaminopyridine) and the adduct was characterized by X-ray crystallography [126]. 68 activates H2
even at −10°C yielding amindogermylamidogermylene 69, both in the solid state and in solution. The structure of 69 was
determined by X-ray crystallography (Scheme 1.5c) [237]. Based on variable temperature NMR experiments at 3–70°C in
THF-d8 solution, it was concluded that in solution germylgermylene 69 is in equilibrium with digermene 70 [237]. The
reaction mechanisms of addition of H2 to R2NE-ENR2 (E=Si, Ge, Sn) were studied computationally by Frenking and
coworkers (for detailed PESs the reader is referred to the cited manuscripts) [225, 238]. The hydrogenation of 68 was cal-
culated (at BP86/def2-TZVPP) to be exergonic, forming either 69 (ΔG = −7.5 kcal/mol, −9.4 kcal/mol including dispersion
effects, and −8.9 kcal/mol when solvent effect is included) or 70 (ΔG = −5.6 kcal/mol, −6.6 kcal/mol including dispersion
effects, and –5.7 kcal/mol, when solvent effect is included). The rate-determining free energy barrier for hydrogenation is
20.4 kcal/mol, 18.4 kcal/mol including dispersion effects, and 19.0 kcal/mol with solvent effect [225]. 69 is more stable than
70 by only 2–3 kcal/mol which is in line with the observed equilibrium between these isomers in solution. r(Ge=Ge) is
2.544 Å (70, calculated) [225], 2.486 Å (22, exp., and 2.510 Å, calc.) [126], and 2.535 Å (23, exp.) [127]. These bonds are at
the longest edge of known Ge=Ge bonds, and are close to that of r(Ge-Ge) in 69 of 2.550 Å [237]. These digermenes are also
highly trans-bent, i.e., by 50° (calculated for 70) [237] (54.1° measured for 22) [126], and by a considerably smaller angle of
39.1° in 23 (exp.) [127]. Computational studies are required for analyzing the nature of the bonding in these molecules.
Scheme 1.5 Synthesis of (E )-(R2N)HGe=GeH(NR2) by hydrogenation of amido-digermylenes

1.4.2.2.2.2 Electropositive Substituents

Electropositive substituents reduce ΔEST of ER2, lower the trans-bending angle of R2E=ER2, and decrease its bond dissoci-
ation energy to the ER2 fragments.
1.4.2.2.2.2.1 Silyl Substituents

The calculated (at UB3LYP/6‑31+G(d,p)//UB3LYP/6‑31+G(d,p) + ZPE) ΔEST for (H3Si)2Si is 8.4 kcal/mol, compared to
20 kcal/mol for SiH2, and it is smaller for bulkier silyl substituents, e.g., ΔEST((Me3Si)2Si) = 2.8 [239]. Thus, H3Si(H)
Si=SiH2 [211] and (H3Si)2Si=Si(SiH3)2 [240] are both calculated to be planar. In tetrasilyldisilene, r(Si=Si) = 2.148 Å.
Isolated disilenes, with bulky silyl substituents, e.g., R3Si(R’3Si)Si=Si(SiR’3)SiR3 (R3Si=SiMe2tBu, R’3Si=SiMeiPr2) (71)
[241] and (R3Si)2Si=Si(SiR3)2 (R3Si=SiMe2tBu) (72) [242] are both planar with r(Si=Si) = 2.196 Å and 2.202 Å, respectively,
and the twist angles about the double bonds are 0° and 8.9°, respectively. Increasing the bulk of the substituents to SiMetBu2
(73) retains the planar geometry, but the double bond is twisted by 54.5°, elongating r(Si=Si) to 2.259 Å [243]. The calcu-
lated structure of 73 (at UBP86-D3/TZVP + D3, including dispersion corrections) [244] is in very good agreement with its
X-ray structure. The significant twist of the double bond enables a facile thermal rotation around the double bond, over-
coming a barrier of only 7.5 kcal/mol to access a triplet biradical that was observed by EPR spectroscopy, and its identity
was supported by calculations [244]. This is the first spectroscopic observation of a triplet diradical resulting from thermal
rotation around an E=E double bond, including C=C bonds.
Similarly to the effect of silyl substitution on silylenes, the calculated singlet-triplet energy gap (ΔEST) of Ge(SiH3)2 is
13.8 kcal/mol (at B3LYP/DZP++) [223], significantly smaller than for GeH2 and Ge(CH3)2 for which ΔEST are 26.7 [223]
(27.5 [212]) and 31.0 [223] (31.5 [212]) kcal/mol, respectively, but larger than for Si(SiH3)2 at 8.4 kcal/mol. The smaller
ΔEST of Ge(SiH3)2 causes a significant decrease in the calculated trans-bending angle θ and in r(Ge=Ge); for example, in
R2Ge=GeR2, R=SiH3, θ = 27.9° and r(Ge=Ge) = 2.292 Å, compared to θ = 41.14° and r(Ge=Ge) = 2.340 Å for R=CH3, and
θ = 43.9° and r(Ge=Ge) = 2.309 Å for R=H (at B3LYP/6-311G(d) [245]; calculated values at other computational levels are
given in Table 1.3 and in Figure 1.10). The silyl effect on geometry is exhibited also in isolated digermenes, e.g., in (iPr2M
eSi)2Ge=Ge(SiMeiPr2)2, (74), (iPr3Si)2Ge=Ge(SiiPr3)2 (75), and (tBuMe2Si)2Ge=Ge(SiMe2tBu)2 (11) in which the trans-
bending angles are: θ = 5.9, 16.4, and 7.5°, and r(Ge=Ge) = 2.268, 2.298, and 2.270 Å, respectively (the twist angle in these
three compounds is 0° [119, 120]), compared to the much larger θ of 32° and longer r(Ge=Ge) of 2.347 Å in [(Me3Si)2CH]2
Ge=Ge[CH(SiMe3)2]2 (1) [86, 87], or in aryl substituted digermenes that have trans-bending angles in the range of 20–40°
[16, 18].
The most significant change in geometry is observed for (tBu2MeSi)2Ge=Ge(SiMetBu2)2, (12) [121b]; i.e., θ = 0°,
r(Ge=Ge) significantly elongated to 2.346 Å, and the twist angle is very large, 52.8°, similarly to that of disilene 73. The
extreme twist reduces the 4pπ–4pπ overlap, destabilizes the HOMO, and decreases the HOMO–LUMO gap (Figure 1.14),
as manifested in a redshift of the UV-Vis absorption to 618 nm [121b] compared to that of 11 (421 nm) and to other iso-
lated digermenes (412–475 nm). The partial breaking of the Ge–Ge π bond in 12 may indicate a contribution of a biradical
character to the bond and a facile rotation to obtain a triplet biradical, as observed in the analogous disilene 73, but a
triplet state rotated digermene analogue has not been yet reported. 12 produces stable cation- and anion-radicals by cyclic
voltammetry [121b].
Figure 1.14 Optimized structure and HOMOs (B3LYP/6-31G(d)) of a set of silyl- substituted digermenes. Reprinted with permission
from Ref. [121b]. Copyright (2014) John Wiley & Sons Inc.
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woman could have worn the helmet and shot the arrow, could have
led troops to attack, ruled with indomitable justice barbarian hordes
and lain under a shield noseless in a church, or made a green grass
mound on some primeval hillside, that woman was Millicent Bruton.
Debarred by her sex and some truancy, too, of the logical faculty
(she found it impossible to write a letter to the Times), she had the
thought of Empire always at hand, and had acquired from her
association with that armoured goddess her ramrod bearing, her
robustness of demeanour, so that one could not figure her even in
death parted from the earth or roaming territories over which, in
some spiritual shape, the Union Jack had ceased to fly. To be not
English even among the dead—no, no! Impossible!
But was it Lady Bruton (whom she used to know)? Was it Peter
Walsh grown grey? Lady Rosseter asked herself (who had been
Sally Seton). It was old Miss Parry certainly—the old aunt who used
to be so cross when she stayed at Bourton. Never should she forget
running along the passage naked, and being sent for by Miss Parry!
And Clarissa! oh Clarissa! Sally caught her by the arm.
Clarissa stopped beside them.
“But I can’t stay,” she said. “I shall come later. Wait,” she said,
looking at Peter and Sally. They must wait, she meant, until all these
people had gone.
“I shall come back,” she said, looking at her old friends, Sally and
Peter, who were shaking hands, and Sally, remembering the past no
doubt, was laughing.
But her voice was wrung of its old ravishing richness; her eyes not
aglow as they used to be, when she smoked cigars, when she ran
down the passage to fetch her sponge bag, without a stitch of
clothing on her, and Ellen Atkins asked, What if the gentlemen had
met her? But everybody forgave her. She stole a chicken from the
larder because she was hungry in the night; she smoked cigars in
her bedroom; she left a priceless book in the punt. But everybody
adored her (except perhaps Papa). It was her warmth; her vitality—
she would paint, she would write. Old women in the village never to
this day forgot to ask after “your friend in the red cloak who seemed
so bright.” She accused Hugh Whitbread, of all people (and there he
was, her old friend Hugh, talking to the Portuguese Ambassador), of
kissing her in the smoking-room to punish her for saying that women
should have votes. Vulgar men did, she said. And Clarissa
remembered having to persuade her not to denounce him at family
prayers—which she was capable of doing with her daring, her
recklessness, her melodramatic love of being the centre of
everything and creating scenes, and it was bound, Clarissa used to
think, to end in some awful tragedy; her death; her martyrdom;
instead of which she had married, quite unexpectedly, a bald man
with a large buttonhole who owned, it was said, cotton mills at
Manchester. And she had five boys!
She and Peter had settled down together. They were talking: it
seemed so familiar—that they should be talking. They would discuss
the past. With the two of them (more even than with Richard) she
shared her past; the garden; the trees; old Joseph Breitkopf singing
Brahms without any voice; the drawing-room wall-paper; the smell of
the mats. A part of this Sally must always be; Peter must always be.
But she must leave them. There were the Bradshaws, whom she
disliked. She must go up to Lady Bradshaw (in grey and silver,
balancing like a sea-lion at the edge of its tank, barking for
invitations, Duchesses, the typical successful man’s wife), she must
go up to Lady Bradshaw and say....
But Lady Bradshaw anticipated her.
“We are shockingly late, dear Mrs. Dalloway, we hardly dared to
come in,” she said.
And Sir William, who looked very distinguished, with his grey hair
and blue eyes, said yes; they had not been able to resist the
temptation. He was talking to Richard about that Bill probably, which
they wanted to get through the Commons. Why did the sight of him,
talking to Richard, curl her up? He looked what he was, a great
doctor. A man absolutely at the head of his profession, very
powerful, rather worn. For think what cases came before him—
people in the uttermost depths of misery; people on the verge of
insanity; husbands and wives. He had to decide questions of
appalling difficulty. Yet—what she felt was, one wouldn’t like Sir
William to see one unhappy. No; not that man.
“How is your son at Eton?” she asked Lady Bradshaw.
He had just missed his eleven, said Lady Bradshaw, because of the
mumps. His father minded even more than he did, she thought
“being,” she said, “nothing but a great boy himself.”
Clarissa looked at Sir William, talking to Richard. He did not look like
a boy—not in the least like a boy. She had once gone with some one
to ask his advice. He had been perfectly right; extremely sensible.
But Heavens—what a relief to get out to the street again! There was
some poor wretch sobbing, she remembered, in the waiting-room.
But she did not know what it was—about Sir William; what exactly
she disliked. Only Richard agreed with her, “didn’t like his taste,
didn’t like his smell.” But he was extraordinarily able. They were
talking about this Bill. Some case, Sir William was mentioning,
lowering his voice. It had its bearing upon what he was saying about
the deferred effects of shell shock. There must be some provision in
the Bill.
Sinking her voice, drawing Mrs. Dalloway into the shelter of a
common femininity, a common pride in the illustrious qualities of
husbands and their sad tendency to overwork, Lady Bradshaw (poor
goose—one didn’t dislike her) murmured how, “just as we were
starting, my husband was called up on the telephone, a very sad
case. A young man (that is what Sir William is telling Mr. Dalloway)
had killed himself. He had been in the army.” Oh! thought Clarissa, in
the middle of my party, here’s death, she thought.
She went on, into the little room where the Prime Minister had gone
with Lady Bruton. Perhaps there was somebody there. But there was
nobody. The chairs still kept the impress of the Prime Minister and
Lady Bruton, she turned deferentially, he sitting four-square,
authoritatively. They had been talking about India. There was
nobody. The party’s splendour fell to the floor, so strange it was to
come in alone in her finery.
What business had the Bradshaws to talk of death at her party? A
young man had killed himself. And they talked of it at her party—the
Bradshaws talked of death. He had killed himself—but how? Always
her body went through it first, when she was told, suddenly, of an
accident; her dress flamed, her body burnt. He had thrown himself
from a window. Up had flashed the ground; through him, blundering,
bruising, went the rusty spikes. There he lay with a thud, thud, thud
in his brain, and then a suffocation of blackness. So she saw it. But
why had he done it? And the Bradshaws talked of it at her party!
She had once thrown a shilling into the Serpentine, never anything
more. But he had flung it away. They went on living (she would have
to go back; the rooms were still crowded; people kept on coming).
They (all day she had been thinking of Bourton, of Peter, of Sally),
they would grow old. A thing there was that mattered; a thing,
wreathed about with chatter, defaced, obscured in her own life, let
drop every day in corruption, lies, chatter. This he had preserved.
Death was defiance. Death was an attempt to communicate; people
feeling the impossibility of reaching the centre which, mystically,
evaded them; closeness drew apart; rapture faded, one was alone.
There was an embrace in death.
But this young man who had killed himself—had he plunged holding
his treasure? “If it were now to die, ’twere now to be most happy,”
she had said to herself once, coming down in white.
Or there were the poets and thinkers. Suppose he had had that
passion, and had gone to Sir William Bradshaw, a great doctor yet to
her obscurely evil, without sex or lust, extremely polite to women, but
capable of some indescribable outrage—forcing your soul, that was
it—if this young man had gone to him, and Sir William had
impressed him, like that, with his power, might he not then have said
(indeed she felt it now), Life is made intolerable; they make life
intolerable, men like that?
Then (she had felt it only this morning) there was the terror; the
overwhelming incapacity, one’s parents giving it into one’s hands,
this life, to be lived to the end, to be walked with serenely; there was
in the depths of her heart an awful fear. Even now, quite often if
Richard had not been there reading the Times, so that she could
crouch like a bird and gradually revive, send roaring up that
immeasurable delight, rubbing stick to stick, one thing with another,
she must have perished. But that young man had killed himself.
Somehow it was her disaster—her disgrace. It was her punishment
to see sink and disappear here a man, there a woman, in this
profound darkness, and she forced to stand here in her evening
dress. She had schemed; she had pilfered. She was never wholly
admirable. She had wanted success. Lady Bexborough and the rest
of it. And once she had walked on the terrace at Bourton.
It was due to Richard; she had never been so happy. Nothing could
be slow enough; nothing last too long. No pleasure could equal, she
thought, straightening the chairs, pushing in one book on the shelf,
this having done with the triumphs of youth, lost herself in the
process of living, to find it, with a shock of delight, as the sun rose,
as the day sank. Many a time had she gone, at Bourton when they
were all talking, to look at the sky; or seen it between people’s
shoulders at dinner; seen it in London when she could not sleep.
She walked to the window.
It held, foolish as the idea was, something of her own in it, this
country sky, this sky above Westminster. She parted the curtains;
she looked. Oh, but how surprising!—in the room opposite the old
lady stared straight at her! She was going to bed. And the sky. It will
be a solemn sky, she had thought, it will be a dusky sky, turning
away its cheek in beauty. But there it was—ashen pale, raced over
quickly by tapering vast clouds. It was new to her. The wind must
have risen. She was going to bed, in the room opposite. It was
fascinating to watch her, moving about, that old lady, crossing the
room, coming to the window. Could she see her? It was fascinating,
with people still laughing and shouting in the drawing-room, to watch
that old woman, quite quietly, going to bed. She pulled the blind now.
The clock began striking. The young man had killed himself; but she
did not pity him; with the clock striking the hour, one, two, three, she
did not pity him, with all this going on. There! the old lady had put out
her light! the whole house was dark now with this going on, she
repeated, and the words came to her, Fear no more the heat of the
sun. She must go back to them. But what an extraordinary night! She
felt somehow very like him—the young man who had killed himself.
She felt glad that he had done it; thrown it away. The clock was
striking. The leaden circles dissolved in the air. He made her feel the
beauty; made her feel the fun. But she must go back. She must
assemble. She must find Sally and Peter. And she came in from the
little room.
“But where is Clarissa?” said Peter. He was sitting on the sofa with
Sally. (After all these years he really could not call her “Lady
Rosseter.”) “Where’s the woman gone to?” he asked. “Where’s
Clarissa?”
Sally supposed, and so did Peter for the matter of that, that there
were people of importance, politicians, whom neither of them knew
unless by sight in the picture papers, whom Clarissa had to be nice
to, had to talk to. She was with them. Yet there was Richard
Dalloway not in the Cabinet. He hadn’t been a success, Sally
supposed? For herself, she scarcely ever read the papers. She
sometimes saw his name mentioned. But then—well, she lived a
very solitary life, in the wilds, Clarissa would say, among great
merchants, great manufacturers, men, after all, who did things. She
had done things too!
“I have five sons!” she told him.
Lord, Lord, what a change had come over her! the softness of
motherhood; its egotism too. Last time they met, Peter remembered,
had been among the cauliflowers in the moonlight, the leaves “like
rough bronze” she had said, with her literary turn; and she had
picked a rose. She had marched him up and down that awful night,
after the scene by the fountain; he was to catch the midnight train.
Heavens, he had wept!
That was his old trick, opening a pocket-knife, thought Sally, always
opening and shutting a knife when he got excited. They had been
very, very intimate, she and Peter Walsh, when he was in love with
Clarissa, and there was that dreadful, ridiculous scene over Richard
Dalloway at lunch. She had called Richard “Wickham.” Why not call
Richard “Wickham”? Clarissa had flared up! and indeed they had
never seen each other since, she and Clarissa, not more than half a
dozen times perhaps in the last ten years. And Peter Walsh had
gone off to India, and she had heard vaguely that he had made an
unhappy marriage, and she didn’t know whether he had any
children, and she couldn’t ask him, for he had changed. He was
rather shrivelled-looking, but kinder, she felt, and she had a real
affection for him, for he was connected with her youth, and she still
had a little Emily Brontë he had given her, and he was to write,
surely? In those days he was to write.
“Have you written?” she asked him, spreading her hand, her firm and
shapely hand, on her knee in a way he recalled.
“Not a word!” said Peter Walsh, and she laughed.
She was still attractive, still a personage, Sally Seton. But who was
this Rosseter? He wore two camellias on his wedding day—that was
all Peter knew of him. “They have myriads of servants, miles of
conservatories,” Clarissa wrote; something like that. Sally owned it
with a shout of laughter.
“Yes, I have ten thousand a year”—whether before the tax was paid
or after, she couldn’t remember, for her husband, “whom you must
meet,” she said, “whom you would like,” she said, did all that for her.
And Sally used to be in rags and tatters. She had pawned her
grandmother’s ring which Marie Antoinette had given her great-
grandfather to come to Bourton.
Oh yes, Sally remembered; she had it still, a ruby ring which Marie
Antoinette had given her great-grandfather. She never had a penny
to her name in those days, and going to Bourton always meant some
frightful pinch. But going to Bourton had meant so much to her—had
kept her sane, she believed, so unhappy had she been at home. But
that was all a thing of the past—all over now, she said. And Mr. Parry
was dead; and Miss Parry was still alive. Never had he had such a
shock in his life! said Peter. He had been quite certain she was dead.
And the marriage had been, Sally supposed, a success? And that
very handsome, very self-possessed young woman was Elizabeth,
over there, by the curtains, in red.
(She was like a poplar, she was like a river, she was like a hyacinth,
Willie Titcomb was thinking. Oh how much nicer to be in the country
and do what she liked! She could hear her poor dog howling,
Elizabeth was certain.) She was not a bit like Clarissa, Peter Walsh
said.
“Oh, Clarissa!” said Sally.
What Sally felt was simply this. She had owed Clarissa an enormous
amount. They had been friends, not acquaintances, friends, and she
still saw Clarissa all in white going about the house with her hands
full of flowers—to this day tobacco plants made her think of Bourton.
But—did Peter understand?—she lacked something. Lacked what
was it? She had charm; she had extraordinary charm. But to be frank
(and she felt that Peter was an old friend, a real friend—did absence
matter? did distance matter? She had often wanted to write to him,
but torn it up, yet felt he understood, for people understand without
things being said, as one realises growing old, and old she was, had
been that afternoon to see her sons at Eton, where they had the
mumps), to be quite frank then, how could Clarissa have done it?—
married Richard Dalloway? a sportsman, a man who cared only for
dogs. Literally, when he came into the room he smelt of the stables.
And then all this? She waved her hand.
Hugh Whitbread it was, strolling past in his white waistcoat, dim, fat,
blind, past everything he looked, except self-esteem and comfort.
“He’s not going to recognise us,” said Sally, and really she hadn’t the
courage—so that was Hugh! the admirable Hugh!
“And what does he do?” she asked Peter.
He blacked the King’s boots or counted bottles at Windsor, Peter told
her. Peter kept his sharp tongue still! But Sally must be frank, Peter
said. That kiss now, Hugh’s.
On the lips, she assured him, in the smoking-room one evening. She
went straight to Clarissa in a rage. Hugh didn’t do such things!
Clarissa said, the admirable Hugh! Hugh’s socks were without
exception the most beautiful she had ever seen—and now his
evening dress. Perfect! And had he children?
“Everybody in the room has six sons at Eton,” Peter told her, except
himself. He, thank God, had none. No sons, no daughters, no wife.
Well, he didn’t seem to mind, said Sally. He looked younger, she
thought, than any of them.
But it had been a silly thing to do, in many ways, Peter said, to marry
like that; “a perfect goose she was,” he said, but, he said, “we had a
splendid time of it,” but how could that be? Sally wondered; what did
he mean? and how odd it was to know him and yet not know a single
thing that had happened to him. And did he say it out of pride? Very
likely, for after all it must be galling for him (though he was an oddity,
a sort of sprite, not at all an ordinary man), it must be lonely at his
age to have no home, nowhere to go to. But he must stay with them
for weeks and weeks. Of course he would; he would love to stay with
them, and that was how it came out. All these years the Dalloways
had never been once. Time after time they had asked them. Clarissa
(for it was Clarissa of course) would not come. For, said Sally,
Clarissa was at heart a snob—one had to admit it, a snob. And it
was that that was between them, she was convinced. Clarissa
thought she had married beneath her, her husband being—she was
proud of it—a miner’s son. Every penny they had he had earned. As
a little boy (her voice trembled) he had carried great sacks.
(And so she would go on, Peter felt, hour after hour; the miner’s son;
people thought she had married beneath her; her five sons; and
what was the other thing—plants, hydrangeas, syringas, very, very
rare hibiscus lilies that never grow north of the Suez Canal, but she,
with one gardener in a suburb near Manchester, had beds of them,
positively beds! Now all that Clarissa had escaped, unmaternal as
she was.)
A snob was she? Yes, in many ways. Where was she, all this time? It
was getting late.
“Yet,” said Sally, “when I heard Clarissa was giving a party, I felt I
couldn’t not come—must see her again (and I’m staying in Victoria
Street, practically next door). So I just came without an invitation.
But,” she whispered, “tell me, do. Who is this?”
It was Mrs. Hilbery, looking for the door. For how late it was getting!
And, she murmured, as the night grew later, as people went, one
found old friends; quiet nooks and corners; and the loveliest views.
Did they know, she asked, that they were surrounded by an
enchanted garden? Lights and trees and wonderful gleaming lakes
and the sky. Just a few fairy lamps, Clarissa Dalloway had said, in
the back garden! But she was a magician! It was a park.... And she
didn’t know their names, but friends she knew they were, friends
without names, songs without words, always the best. But there
were so many doors, such unexpected places, she could not find her
way.
“Old Mrs. Hilbery,” said Peter; but who was that? that lady standing
by the curtain all the evening, without speaking? He knew her face;
connected her with Bourton. Surely she used to cut up underclothes
at the large table in the window? Davidson, was that her name?
“Oh, that is Ellie Henderson,” said Sally. Clarissa was really very
hard on her. She was a cousin, very poor. Clarissa was hard on
people.
She was rather, said Peter. Yet, said Sally, in her emotional way, with
a rush of that enthusiasm which Peter used to love her for, yet
dreaded a little now, so effusive she might become—how generous
to her friends Clarissa was! and what a rare quality one found it, and
how sometimes at night or on Christmas Day, when she counted up
her blessings, she put that friendship first. They were young; that
was it. Clarissa was pure-hearted; that was it. Peter would think her
sentimental. So she was. For she had come to feel that it was the
only thing worth saying—what one felt. Cleverness was silly. One
must say simply what one felt.
“But I do not know,” said Peter Walsh, “what I feel.”
Poor Peter, thought Sally. Why did not Clarissa come and talk to
them? That was what he was longing for. She knew it. All the time he
was thinking only of Clarissa, and was fidgeting with his knife.
He had not found life simple, Peter said. His relations with Clarissa
had not been simple. It had spoilt his life, he said. (They had been so
intimate—he and Sally Seton, it was absurd not to say it.) One could
not be in love twice, he said. And what could she say? Still, it is
better to have loved (but he would think her sentimental—he used to
be so sharp). He must come and stay with them in Manchester. That
is all very true, he said. All very true. He would love to come and stay
with them, directly he had done what he had to do in London.
And Clarissa had cared for him more than she had ever cared for
Richard. Sally was positive of that.
“No, no, no!” said Peter (Sally should not have said that—she went
too far). That good fellow—there he was at the end of the room,
holding forth, the same as ever, dear old Richard. Who was he
talking to? Sally asked, that very distinguished-looking man? Living
in the wilds as she did, she had an insatiable curiosity to know who
people were. But Peter did not know. He did not like his looks, he
said, probably a Cabinet Minister. Of them all, Richard seemed to
him the best, he said—the most disinterested.
“But what has he done?” Sally asked. Public work, she supposed.
And were they happy together? Sally asked (she herself was
extremely happy); for, she admitted, she knew nothing about them,
only jumped to conclusions, as one does, for what can one know
even of the people one lives with every day? she asked. Are we not
all prisoners? She had read a wonderful play about a man who
scratched on the wall of his cell, and she had felt that was true of life
—one scratched on the wall. Despairing of human relationships
(people were so difficult), she often went into her garden and got
from her flowers a peace which men and women never gave her. But
no; he did not like cabbages; he preferred human beings, Peter said.
Indeed, the young are beautiful, Sally said, watching Elizabeth cross
the room. How unlike Clarissa at her age! Could he make anything of
her? She would not open her lips. Not much, not yet, Peter admitted.
She was like a lily, Sally said, a lily by the side of a pool. But Peter
did not agree that we know nothing. We know everything, he said; at
least he did.
But these two, Sally whispered, these two coming now (and really
she must go, if Clarissa did not come soon), this distinguished-
looking man and his rather common-looking wife who had been
talking to Richard—what could one know about people like that?
“That they’re damnable humbugs,” said Peter, looking at them
casually. He made Sally laugh.
But Sir William Bradshaw stopped at the door to look at a picture. He
looked in the corner for the engraver’s name. His wife looked too. Sir
William Bradshaw was so interested in art.
When one was young, said Peter, one was too much excited to know
people. Now that one was old, fifty-two to be precise (Sally was fifty-
five, in body, she said, but her heart was like a girl’s of twenty); now
that one was mature then, said Peter, one could watch, one could
understand, and one did not lose the power of feeling, he said. No,
that is true, said Sally. She felt more deeply, more passionately,
every year. It increased, he said, alas, perhaps, but one should be
glad of it—it went on increasing in his experience. There was some
one in India. He would like to tell Sally about her. He would like Sally
to know her. She was married, he said. She had two small children.
They must all come to Manchester, said Sally—he must promise
before they left.
There’s Elizabeth, he said, she feels not half what we feel, not yet.
But, said Sally, watching Elizabeth go to her father, one can see they
are devoted to each other. She could feel it by the way Elizabeth
went to her father.
For her father had been looking at her, as he stood talking to the
Bradshaws, and he had thought to himself, Who is that lovely girl?
And suddenly he realised that it was his Elizabeth, and he had not
recognised her, she looked so lovely in her pink frock! Elizabeth had
felt him looking at her as she talked to Willie Titcomb. So she went to
him and they stood together, now that the party was almost over,
looking at the people going, and the rooms getting emptier and
emptier, with things scattered on the floor. Even Ellie Henderson was
going, nearly last of all, though no one had spoken to her, but she
had wanted to see everything, to tell Edith. And Richard and
Elizabeth were rather glad it was over, but Richard was proud of his
daughter. And he had not meant to tell her, but he could not help
telling her. He had looked at her, he said, and he had wondered,
Who is that lovely girl? and it was his daughter! That did make her
happy. But her poor dog was howling.
“Richard has improved. You are right,” said Sally. “I shall go and talk
to him. I shall say good-night. What does the brain matter,” said Lady
Rosseter, getting up, “compared with the heart?”
“I will come,” said Peter, but he sat on for a moment. What is this
terror? what is this ecstasy? he thought to himself. What is it that fills
me with extraordinary excitement?
It is Clarissa, he said.
For there she was.
THE END
Transcriber’s note
Minor punctuation errors have been changed
without notice. Inconsistencies in hyphenation have
been standardized. The following printer errors have
been changed.
CHANGED FROM TO
“word poetry of “word of poetry
Page 159:
herself” herself”
“lent a little “leant a little
Page 248:
forward” forward”
All other inconsistencies are as in the original.
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Organogermanium Compounds Theory Experiment and Applications Vladimir Ya Lee Full Chapter

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Organogermanium Compounds Theory Experiment and Applications Vladimir Ya Lee Full Chapter

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Organogermanium Compounds.

Theory, Experiment, and Applications

Theory, Experiment, and Applications

Edited by Vladimir Ya. Lee

Limit of Liability/Disclaimer of Warranty

Cover Images: © ALFRED PASIEKA/Getty Images; © Intothelight Photography/Shutterstock

Full Table of Contents

2 Organogermanium Compounds of the Main Group Elements 103

3 Transition Metal Complexes of Germanium 195

4 Germanium Cages and Clusters 225

5 Arylgermanium Hydrides, ArnGeH4-n (n = 1–3) - Synthesis, Characterization, Reactivity 277

6 Germylium Ions and Germylium Ion-like Species 299

7 Germanium-Containing Radicals 339

8 Germanium-Centered Anions 361

10 Multiple Bonds to Germanium 435

11 Germaaromatic Compounds 477

12 Germanium-centered Ion Radicals 507

13 Donor-acceptor Stabilization of Species with Low-coordinate Germanium 561

14 Synthesis of the Penta- and Hexacoordinate Germanium(IV) Complexes 597

15 Dynamic Stereochemistry of Penta- and Hexacoordinate Germanium(IV) Complexes 629

16 X-ray Crystallography of Organogermanium Compounds 667

17 Organogermanium Photochemistry 745

18 Oligo- and Polygermanes 787

19 Bioorganic and Medicinal Organogermanium Chemistry 839

2 Organogermanium Compounds of the Main Group Elements 103

3 Transition Metal Complexes of Germanium 195

4 Germanium Cages and Clusters 225

5 Arylgermanium Hydrides, ArnGeH4-n (n = 1–3) - Synthesis, Characterization, Reactivity 277

6 Germylium Ions and Germylium Ion-like Species 299

7 Germanium-Containing Radicals 339

8 Germanium-Centered Anions 361

10 Multiple Bonds to Germanium 435

Vladimir Ya. Lee (Editor)

Yitzhak Apeloig Miriam Karni

Frank Breher Tanja Kunz

Mikhail P. Egorov Alexander A. Korlyukov

Vladimir Ya. Lee

Naokazu Kano Thomas Müller

Takashi Nakamura Sakya S. Sen

Kohtaro Osakada Ana Torvisco

Herbert W. Roesky Frank Uhlig

Andreas Schnepf Kirill V. Zaitsev

Computational and Theoretical Aspects of Structure and Bonding in Doubly

Miriam Karni and Yitzhak Apeloig

HOMO highest occupied molecular orbital

RRKM Rice-Ramsberger-Kassel-Marcus theory

Table 1.1 Selected physical properties of group 14 elements.

For the transition: ns2np2(3P) → ns1np2(4P);

For the transition: ns2np2(3P) → ns2np1(2P);

1.2 Computational Methods

1.2.1 Ab initio Methods

1.2.2 Density Functional Theory ( DFT) Methods

1.2.3 Methods for Analysis of Electronic Structure

1.2.4 How Important are Relativistic Effects for Ge?

Bond length relative to NR (a.u)

1.3 Historical Overview

Scheme 1.1 Mode of interactions of two stannylenes producing a trans-bent distannene.

Twist angle UV-Vis

25 ArBrGe=GeBrAr a) 2.509 a) 44.6b a) No twist b) 449 [129,130] 2005,

26 Bbt r(Ge=Ge) = 2.413 – 494 [131] 2015

Twist angle UV-Vis

27 Bbt Bbt 2.414 – NA [132] 2018

28 Tbb Tbb r(Ge=Ge) = 2.416 351.3 – 369 [130] 2016

¼ Eσ+π ≤ ∆EST ≤ ½ Eσ+π (1.1)