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Handbook of Chalcogen Chemistry
New Perspectives in Sulfur, Selenium and Tellurium
 To my delightful
grandchildren
Francesco and Silvia
Handbook of Chalcogen
Chemistry
New Perspectives in Sulfur, Selenium and Tellurium

Edited by

Francesco A. Devillanova
Department of Inorganic and Analytical Chemistry, University of
Cagliari, Italy
The cover image is reproduced with the permission from Wileys-VCH and from the
authors. Taken from: A. Haas, J. Kasprowski and M. Pryka, Chem. Ber. 1992, 125, 789.

ISBN-10: 0-85404-366-7
ISBN-13: 978-0-85404-366-8

A catalogue record for this book is available from the British Library

r The Royal Society of Chemistry 2007

All rights reserved

Apart from any fair dealing for the purpose of research or private study for
non-commercial purposes, or criticism or review as permitted under the terms of the UK
Copyright, Designs and Patents Act, 1988 and the Copyright and Related Rights
Regulations 2003, this publication may not be reproduced, stored or transmitted, in any
form or by any means, without the prior permission in writing of The Royal Society of
Chemistry, or in the case of reprographic reproduction only in accordance with the terms
of the licences issued by the Copyright Licensing Agency in the UK, or in accordance with
the terms of the licences issued by the appropriate Reproduction Rights Organization
outside the UK. Enquiries concerning reproduction outside the terms stated here should
be sent to The Royal Society of Chemistry at the address printed on this page.

Published by The Royal Society of Chemistry,

Thomas Graham House, Science Park, Milton Road,
Cambridge CB4 0WF, UK

Registered Charity Number 207890

For further information see our web site at www.rsc.org

Typeset by Macmillan India Ltd, Bangalore, India

Printed and bound by Henry Ling Ltd, Dorchester, Dorset, UK
Preface

Up to a few decades ago, chalcogen chemistry was centred almost exclusively

on sulfur, selenium being marginal compared to it and the chemistry of
tellurium being practically inexistent. For many years the chemistry of Se
and Te has grown rapidly: this is easily seen with an electronic search on
SCIfinder comparing 1941–1950 and 1991–2000 and using as entries ‘‘sulfur/
selenium/tellurium compounds’’. The percentage of papers on Se/Te rises from
13.4% (on a total 335 papers) for the former period to 27.7% (on a total 1905
papers) for the latter. A number of factors have contributed to this increase in
the interest in the chemistry of Se and Te. One is the development of new
suitable synthetic methodologies that avoid the use of obnoxious reagents
(CSe2, H2Se, etc.), but most importantly the great variety of technological
applications that can be found for their many compounds. To this purpose I
would like to recall that compounds from the class of the charge-transfer salts
of chalcogen-rich molecules, such as tetrathiafulvalene (TTF), or from that of
1,2-dichalcogenolenes, or the variegated area of metal chalcogenides are
extremely important in Materials Science for their potential applications, which
span from n-dimensional molecular conductors to magnets, to bistable switch-
able materials, and to NLO materials, to quote only a few. Further examples of
this increasing trend, which is always of great topical interest, are the funda-
mental research works in the field of coordination chemistry with a large
variety of ligands containing chalcogen atoms for the preparation of new
precursors for metal–chalcogenide vapour deposition, of metalloenzymes con-
taining multimetallic centres as active sites for a number of catalytic reactions,
or of chalcogen-containing mixed macrocycles with signalling functional
groups as sensors for heavy metal-ion recognition, and so forth.
The simplest way of organizing a handbook that contained an incredible
amount of results from research on chalcogen chemistry while avoiding to omit
important topics appeared to me that of considering the chemistry of chalcogen
elements in combination with all other elements of the periodic table. On the
other hand, an ambitious purpose of the book was to point out the increasing
role of chalcogen elements in multidisciplinar fields such as biochemistry and
materials science. For these reasons, the Handbook of Chalcogen (S, Se, Te)
Chemistry was structured on a multidisciplinary approach by putting together
contributions ranging from organic to inorganic and analytical chemistry,
synthetic to structural and theoretical chemistry, biological to material and
supramolecular chemistry. It was then divided into two parts: in the first of

v
vi Preface
these the chapters are identified by the elements that are bonded to the
chalcogen atoms, from boron to the halogens, including the chalcogens
themselves. The overview ends with two chapters on metal–chalcogenides
and metal–polychalcogenides. The second part of the book includes peculiar
aspects of chalcogen chemistry that represent attractive fields of research in
biological, materials and supramolecular chemistry, as well as a few miscella-
neous chapters on particular topics. When different leitmotivs are considered in
organizing the same subject matter, one still runs the risk of overlaps among the
different chapters even though great care is devoted to avoid this negative
aspect. There is one positive aspect, however, which outbalances the negative
one: i.e., the two parts are strictly interrelated, since the chapters in the second
part are further developments of those in the first part. Thus, the chapter on the
chalcogen–nitrogen bond (Chapter 4) has its counterpart in the one on stable
radicals (Chapter 12.1), where it is clearly shown that fundamental research on
chalcogen–nitrogen compounds can open unthinkable perspectives for the use
of organic radicals in building magnetic materials. Similarly, the chapters on
the chalcogenolate (Chapter 2.1) and 1,1-dichalcogenate (Chapter 10.2) ligands
show that their coordination chemistry is always topical and widely exploited
for potential applications in many different fields, such as that of preparing
enzyme mimetic models (Chapter 11.2). The chapters on chalcogen-rich donors
(Chapter 12.2) and on dithiolenes (Chapter 12.3) can be considered a con-
tinuation of those on chalcogen–carbon compounds: many compounds of both
classes have found a large number of technological applications thanks to their
conducting, magnetic, and optical properties. For this reason, both classes of
compounds have strongly contributed to the increasing interest in chalcogen
chemistry. In the same way, some important technological applications that
have been found for a number of metal chalcogenides (Chapter 9.1) and
polychalcogenides (Chapter 9.2) together with their remarkable diversity in
their structure and properties have been the driving force of the incredible
expansion of these areas of research. The ability of chalcogen elements to
catenate is responsible for the great variety of molecular forms of chalcogen
elements, of their cations (Chapter 7.1) and anions (Chapter 9.2), of their
organic di- and poly-chalcogenides, and of their organic multication species
(Chapter 7.2). Finally, the chalcogen-halogen compounds, both binary (Chap-
ter 8.1) and those that derive from reactions of a variety of chalcogen-
containing donors with halogens/interhalogens (Chapter 8.2), which are ex-
tensively dealt with in the first part of the book, appear consistently in the
second part, as they provide interesting examples of hypervalency of the
chalcogen elements (Chapter 10.3) and represent attractive examples of supra-
molecular structures (Chapter 13) built thanks to the ability of chalcogen-
halogen bonds to give directional secondary bonds, in competition with other
interactions (hydrogen bonding, dipole-dipole interactions, etc.).
Though not exhaustive, the book includes mainly the results of the last
decade and illustrates the tendencies of the most appealing research work.
Particular attention has been paid by the authors to update the literature
almost up to the end of 2005.
Preface vii
The book is a candidate to become a reference book for future years. The
multidisciplinary approach, with chapters reserved to biological, materials, and
supramolecular chemistry, presents the book as an important source of
information not only for chemists but also for physicists, biochemists, and
other researchers, who in some way deal with chalcogen compounds. I hope the
book may induce some curiosity in the reader and attract him towards this kind
of chemistry.
I am greatly indebted to all authors for their commitment and to my
collaborators for useful discussions.
Contents
Chapter 1 Compounds Containing the Boron–Chalcogen B–E
(E¼S, Se, Te) Bond 1
Michael A. Beckett

1.1 Introduction 1
1.2 Books and Review Articles 1
1.3 Polyhedral Boron Hydride Derivatives 2
1.3.1 Species with Exo B–Chalcogen Bonds 2
1.3.2 Species with Chalcogen Atoms within the Cage 8
1.4 Binary, Ternary, and Quarternary Chalcogenoborates 14
1.5 Heterocycles Containing B–E Linkages 17
1.6 Miscellaneous Boron-Chalcogen Compounds and
Reagents 19
Abbreviations 22
References 22

COMPOUNDS CONTAINING THE CARBON-CHALCOGEN

C–E BOND (E¼S, Se, Te)

Chapter 2.1 Thiolates, Selenolates, and Tellurolates 33

M. Concepción Gimeno

2.1.1 Introduction 33
2.1.2 Synthetic Routes of Ligands and Metal
Chalcogenolates 34
2.1.2.1 Synthesis of the Chalcogenols 34
2.1.2.2 Synthesis of Metal Chalcogenolates 34
2.1.3 Alkali and Alkaline Earth Derivatives 36
2.1.4 Main Group Metal Derivatives 39
2.1.4.1 Zinc, Cadmium, and Mercury 39
2.1.4.2 Aluminium, Gallium, Indium, and
Thallium 41
2.1.4.3 Antimony and Bismuth 42
2.1.4.4 Germanium, Tin, and Lead 43

ix
x Contents
2.1.5 Transition Metal Derivatives 44
2.1.5.1 Early Transition Metals 44
2.1.5.2 Chromium, Molybdenum, and Tungsten 45
2.1.5.3 Manganese, Technetium, and Rhenium 46
2.1.5.4 Iron, Ruthenium, and Osmium 47
2.1.5.5 Cobalt, Rhodium, and Iridium 49
2.1.5.6 Nickel, Palladium, and Platinum 51
2.1.5.7 Copper, Silver, and Gold 53
2.1.6 Rare Earth Derivatives 55
2.1.7 Conclusions 57
Acknowledgements 57
References 57

Chapter 2.2 Recent Developments in the Chemistry of

Thio-, Seleno- and Telluro-ethers 81
William Levason and Gillian Reid

2.2.1 Introduction 81
2.2.2 Synthesis 83
2.2.2.1 Monodentates 83
2.2.2.2 Bi- and Polydentates 83
2.2.2.3 Macrocycles 85
2.2.3 Coordination Chemistry of Thio-, Seleno- and
Telluroethers 91
2.2.4 Coordination Modes 92
2.2.4.1 Acyclic Ligands 92
2.2.4.2 Macrocyclic Ligands 94
2.2.5 Applications 99
Acknowledgements 100
References 100

Chapter 2.3 Chalcogenone C¼E compounds 107

Norbert Kuhn and Gaetano Verani

2.3.1 Introduction 107

2.3.2 Thioketones (Thiones) 110
2.3.2.1 Syntheses 110
2.3.2.2 Reactivity 114
2.3.3 Selenoketones (Selones) 121
2.3.3.1 Syntheses 121
2.3.3.2 Reactivity 126
2.3.4 Telluroketones (Tellones) 131
2.3.4.1 Syntheses 131
2.3.4.2 Reactivity 133
References 134
Contents xi
Chapter 2.4 Thioamides, Thioureas and Related Selenium and Tellurium
Compounds 145
Mamoru Koketsu and Hideharu Ishihara

2.4.1 Introduction 145

2.4.2 Thioamides 145
2.4.2.1 Synthesis of Thioamides 146
2.4.2.2 Heterocycles Using Thioamides 151
2.4.2.3 Transformation of Thioamides 156
2.4.2.4 Calculations 160
2.4.2.5 Biological Activities 160
2.4.3 Thioureas 160
2.4.3.1 Synthesis of Thioureas 160
2.4.3.2 Heterocycles Using Thioureas 165
2.4.3.3 Transformation of Thioureas 169
2.4.3.4 Application as Sensor 171
2.4.3.5 Application as Ligand 172
2.4.3.6 Glycosyl Thioureas 172
2.4.3.7 Biological Activities 172
2.4.4 Cyclic Chalcogenoureas 173
2.4.5 Selenoamides and Selenoureas 177
2.4.5.1 Synthesis of Selenoamides and Selenoureas 178
2.4.5.2 Heterocycles Using Selenoamides and
Selenoureas 180
2.4.6 Telluroamides and Telluroureas 181
References 182

Chapter 3 The Compounds Between Si, Ge and Sn and Chalcogens

(S, Se, and Te) Having Both a Single Bond and a Double
Bond (Heavy Ketones) 195
Nobuhiro Takeda, Norihiro Tokitoh and Renji Okazaki

3.1 Introduction 195

3.2 The Compounds Having a Single Bond
between Si, Ge, and Sn and Chalcogens 195
3.2.1 Structural and Spectroscopic Properties 196
3.2.2 Formation of Single Bonds between Heavier
Group 14 and 16 Elements 196
3.2.3 Reactions 202
3.3 The Compounds Having a Double Bond between
Si, Ge, and Sn and Chalcogens (Heavy Ketones) 207
3.3.1 Theoretical Aspects 207
3.3.2 Structural and Spectroscopic Properties 208
3.3.3 Syntheses 211
3.3.4 Reactivities 211
References 215
xii Contents
Chapter 4 Chalcogen–Nitrogen Chemistry 223
Tristram Chivers and Risto S. Laitinen

4.1 Introduction 223

4.2 General Considerations 224
4.3 Characterization of Chalcogen-Nitrogen
Compounds 224
4.3.1 Diffraction Techniques 224
4.3.2 14N and 15N NMR Spectroscopy 226
4.3.3 33S, 77Se and 125Te NMR Spectroscopy 226
4.3.4 ESR Spectroscopy 226
4.3.5 Infrared and Raman Spectroscopy 227
4.4 Binary Chalcogen-Nitrogen Systems 228
4.4.1 Neutral Molecules 228
4.4.2 Cations 231
4.4.3 Anions 233
4.5 Metal Complexes of Binary Chalcogen-Nitrogen
Ligands 235
4.5.1 Thionitrosyl and Selenonitrosyl Complexes 235
4.5.2 Cyclometallathiazenes 236
4.6 Chalcogen-Nitrogen Halides 237
4.6.1 Thiazyl Halides NSX (X=F, Cl, Br) and the
[NSX2]
Anions (X=F, Cl) 237
4.6.2 Thiazyl Trifluoride, NSF3, and Haloimino-
sulfur Difluorides, XNSF2 (X=F, Cl) 238
4.6.3 Acyclic Chalcogen-Nitrogen-Halogen
Cations [N(ECl)2]+ (E=S, Se) and
[N(SeCl2)2]+ 238
4.6.4 Tellurium-Nitrogen-Chlorides [Te4N2Cl8]2+
and Te11N6Cl26 239
4.6.5 Thiodithiazyl and Selenadiselenazyl
Dichloride [E3N2Cl]Cl (E=S, Se) 239
4.6.6 Cyclotrithiazyl Halides (NSX)3 (X=Cl, F) 240
4.6.7 Dihalocyclotetrathiazenes S4N4X2 (X=Cl, F)
and Cyclotetrathiazyl Fluoride (NSF)4 240
4.6.8 Sulfanuric Halides [NS(O)X]2 (X=Cl, F) 241
4.7 Chalcogen-Nitrogen Oxides 241
4.7.1 The Thionyl Imide Anion, [NSO]
241
4.7.2 The Thionitrite and Perthionitrite Anions,
[SNO]
and [SSNO]
242
4.7.3 The [SOxN3]
(x=2, 3) Anions 242
4.7.4 Bis(Sulfinylamino)Chalcogenanes E(NSO)2
(E=S, Se, Te) 242
4.7.5 Cyclic Chalcogen–Nitrogen Oxides 243
4.8 Acyclic Organic Chalcogen-Nitrogen Compounds 244
4.8.1 Chalcogenonitrosyls, RNE (E=S, Se) 244
Contents xiii
4.8.2 Organic Chalcogenylamines RNEO (E=S,
Se, Te) 244
4.8.3 N-Thiosulfinylamines, RNSS 245
4.8.4 Chalcogen Diimides RN=E=NR (E=S,
Se, Te) 246
4.8.5 Imido Chalcogen Halides 248
4.8.6 Triimidochalcogenites, [E(NR)3]2
(E=S,
Se, Te), and Sulfur Triimides, S(NR)3 249
4.8.7 Tetraimidosulfate, [S(NtBu)4]2
, and
Methylenetrimidosulfate, [H2CS(NtBu)3]2
250
4.8.8 Chalcogen Diamides Ex(NR2)2, (E=S, Se, Te;
x=1-4) 250
4.8.9 Organochalcogenyl Azides and Nitrenes 251
4.8.10 S-Nitrosothiols RSNO 252
4.8.11 Trisulfenamides, (RS)3N, and the Radical
[(PhS)2N] 252
4.9 Cyclic Chalcogen Imides 253
4.9.1 Cyclic Sulfur Imides 253
4.9.2 Cyclic Selenium and Tellurium Imides 254
4.10 Carbon-Nitrogen-Chalcogen Ring Systems 255
4.10.1 Five-Membered Rings 255
4.10.2 Six-Membered Rings 258
4.10.3 Seven-Membered Rings 260
4.10.4 Eight-Membered Rings 261
4.10.5 Bicyclic Ring Systems, RCN5S3 262
4.11 Chalcogen-Nitrogen-Phosphorus Ring Systems 263
4.11.1. Chalcogen-Nitrogen-Phosphorus(V) Rings 263
4.11.2 Chalcogen-Nitrogen Rings Containing
Phosphorus(III) or Other p-Block Elements 267
4.12 Chains and Polymers 267
4.12.1 Poly(Sulfur Nitride), (SN)x, and Related
Polymers 267
4.12.2 Sulfur-Nitrogen Chains 269
4.12.3 Sulfur-Nitrogen Polymers Containing
Three-Coordinate Sulfur(IV) 270
4.12.4 Sulfur-Nitrogen Polymers Containing
Four-Coordinate Sulfur(VI) 270
4.13 Outlook 272
References 272

Chapter 5 Chalcogen–Phosphorus (and Heavier Congeners) Chemistry 286

Rob Davies

5.1 Introduction 286

5.2 Preparation, Characterisation and Properties of
Compounds Containing Phosphorus-Chalcogen Bonds 288
xiv Contents
5.2.1 Phosphorus Chalcogenides [PnEm] and
Chalcogeno-Phosphate Anions [PnEm]z
288
5.2.2 Tertiary Phosphine Chalcogenides [R3PE] 291
5.2.3 Diphosphine Di- and Mono-Chalcogenides
[R2P(E)-R 0 -P(E)R2 and R2P(E)-R 0 -PR2] 293
5.2.4 Secondary Phosphine Chalcogenides
[R2P(E)H] 295
5.2.5 Dichalcogenophosphinic Acids (R2PE2H) and
their Derivatives 297
5.2.6 Trichalcogenophosphonic Acids (RPE3H2) and
their Derivatives 300
5.2.7 Amido and Imido Derivatives of Chalcogeno-
Phosphorus Acids 302
5.2.8 Dichalcogenoimido-diphosphinates
[R2P(E)NP(E)R2] 307
5.2.9 Phosphorus-Chalcogen Containing
Heterocycles 309
5.3 Coordination Chemistry of Ligands Containing
Phosphorus-Chalcogen Bonds 312
5.3.1 Phosphorus Chalcogenides (PnEm) and
Chalcogeno-Phosphate Anions [PnEm]z
312
5.3.2 Tertiary Phosphine Chalcogenides
(R3P=E) 314
5.3.3 Diphosphine Di- and Mono-Chalcogenides
[R2P(E)-R 0 -P(E)R2 and R2P(E)-R 0 -PR2] 315
5.3.4 Secondary Phosphine Chalcogenides
(R2PEH) 317
5.3.5 Dichalcogenophosphinic Acids (R2PE2H) and
their Derivatives 318
5.3.6 Trichalcogenophosphonic Acids (RPE3H2) and
their Derivatives 322
5.3.7 Amido and Imido Derivatives of Chalcogeno-
Phosphorus Acids 323
5.3.8 Dichalcogenoimidodiphosphinates
[R2P(E)NHP(E)R2] 326
5.4 Applications of Compounds and Complexes
Containing Phosphorus-Chalcogen Bonds 327
5.4.1 Reactions with Organic Substrates 327
5.4.2 Pesticides and Nerve Agents 330
5.4.3 Precursors Towards Metal Chalcogenide
Thin-Films and Quantum Dots 331
5.4.4 Metal Extraction Technologies 334
5.4.5 Lubricant Additives 334
5.4.6 Other Applications 335
References 335
Contents xv
Chapter 6 Chalcogen–Oxygen Chemistry 344
Mathias S. Wickleder

6.1 Introduction 344

6.2 Binary Sulfur, Selenium, and Tellurium Oxides 344
6.3 Mixed Sulfur, Selenium, and Tellurium Oxides 350
6.4 Oxygen Acids of Sulfur, Selenium, and
Tellurium 351
6.5 Selected Oxo-Chalcogenates 353
6.5.1 Main Group Metals 355
6.5.2 Transition Metals 359
6.5.3 Lanthanides 364
Acknowledgement 369
References 369

COMPOUNDS CONTAINING THE CHALCOGEN–

CHALCOGEN E–E BOND (E ¼ S, SE, TE)

Chapter 7.1 Structure and Bonding of the Neutral Chalcogens and their
Polyatomic Cations 381
Ingo Krossing

7.1.1 Introduction 381

7.1.2 Standard Enthalpies of Formation of the Small
Chalcogen Clusters En (n = 1–8) 382
7.1.3 Structure and Bonding 382
7.1.4 Brief Bonding Introduction 384
7.1.4.1 General Remarks 384
7.1.4.2 np2!ns* Interactions 384
7.1.4.3 p and p*–p* Bonding 385
7.1.5 Polyatomic Chalcogen Molecules or Molecular
Cations 387
7.1.5.1 Molecular E4 Moieties 387
7.1.5.2 Molecular E5 Moieties 388
7.1.5.3 Molecular E6 Moieties 388
7.1.5.4 Molecular E7 Moieties 391
7.1.5.5 Molecular E8 Moieties 393
7.1.5.6 Molecular E9 Moieties 398
7.1.5.7 Molecular E10 Moieties 398
7.1.5.8 Molecular E11–E15 Moieties 399
7.1.5.9 Molecular E17–E20 moieties 401
7.1.6 Polyatomic Chalcogen Polymers and Polymeric
Tellurium Cations 403
7.1.6.1 Fibrous c-S, grey Se and Te 403
xvi Contents
2+
7.1.6.2 Polymers that Contain Te4 Squares: Te4 ,
Te72+ and Te102+ 405
7.1.6.3 A Polymer that Contains Te5 Homocycles:
Te62+ 408
7.1.6.4 Polymers that Contain Te6 Homocycles:
Te72+ and Te82+ 408
7.1.7 Conclusion 411
Acknowledgement 412
References 412

Chapter 7.2 Organochalcogen Multication Species 417

Valentine G. Nenajdenko, Nikolay E. Shevchenko,
Elizabeth S. Balenkova and Igor V. Alabugin

7.2.1 Introduction 417

7.2.2 S–S Dications 418
7.2.2.1 Discovery of Disulfonium Dications 418
7.2.2.2 Synthesis of Disulfonium Dications 419
7.2.2.3 Chemical Properties of Disulfonium
Dications 428
7.2.3 Se–Se, Te–Te and Mixed Dications 435
7.2.4 Trichalcogen–Dications 438
7.2.5 1,4-Dication with Dichalcogen Fragment 441
7.2.6 Polyatomic Chalcogen Dications 443
References 446

HALOGEN–CHALCOGEN X–E (X¼F, Cl, Br, I; E¼S, Se,Te)

CHEMISTRY

Chapter 8.1 Recent Developments in Binary Halogen–Chalcogen

Compounds, Polyanions and Polycations 457
Zhengtao Xu

8.1.1 Introduction 457

8.1.2 Chalcogen Fluorides 458
8.1.3 Chalcogen Chlorides and Bromides 459
8.1.3.1 Selenium and Sulfur Dichlorides 459
8.1.3.2 Disulfur and Diselenium Dihalides 461
8.1.4 Chalcogen Iodides and Tellurium Subhalides 463
8.1.5 Halochalcogenate Anions 465
8.1.6 Halochalcogenate Polycations 469
Acknowledgment 474
References 474
Contents xvii
Chapter 8.2 Charge-Transfer (C.-T.) Adducts and Related Compounds 477
VitoLippolis and Francesco Isaia

8.2.1 Introduction 477

8.2.2 General Aspects of C.-T. Adducts between
Chalcogen-Containing Molecules and Di- and
Inter-Halogens 478
8.2.3 C.-T. "Spoke" Adducts 479
8.2.4 C.-T. "Extended Spoke" Adducts 485
8.2.5 Reactivity of C.-T. Adducts Towards Metal
Powders 490
8.2.5.1 C.-T. Adducts as New Oxidising Reagents 490
8.2.5.2 Oxidation of Metals by C.-T. Adducts of
Sulfur-Donors 491
8.2.5.3 Oxidation of Metals by C.-T. Adducts of
Selenium-Donors 495
8.2.6 Conclusions 495
Acknowledgements 496
References 496

METAL CHALCOGENIDES

Chapter 9.1 Metal Chalcogenides: Clusters, Layers, Nanotubes 503

Maxim N. Sokolov

9.1.1 Introduction 503

9.1.2 Metal Clusters, Chains, Layers 504
9.1.2.1 General Remarks 504
9.1.2.2 Isolated Clusters 505
9.1.2.3 Connected and Condensed Clusters 511
9.1.2.4 Metal Chains 517
9.1.2.5 Metal Layers 521
9.1.2.6 Three-Dimensional Metal Frameworks 522
9.1.3 Nanotubes 523
Acknowledgment 529
References 529

Chapter 9.2 Polychalcogenides 543

William S. Sheldrick

9.2.1 Introduction 543

9.2.2 Polychalcogenide Anions 545
9.2.2.1 Synthesis and Speciation 545
9.2.2.2. Polysulfides 546
xviii Contents
9.2.2.3. Polyselenides 548
9.2.2.4. Polytellurides 551
9.2.2.5. Thio- and Selenidotellurates 557
9.2.3 Complexes of Polychalcogenide
Ligands 558
9.2.3.1. Synthesis 558
9.2.3.2. Terminal and Bridging Modes 560
9.2.3.3. Side-On and Chelating Modes 565
9.2.3.4. Polymeric Ligands 567
9.2.4. Note Added in Proof 568
References 569

MISCELLANEOUS ASPECTS

Chapter 10.1 Synthesis and Stereochemistry of Optically Active

Chalcogen Compounds 577
Toshio Shimizu and Nobumasa Kamigata

10.1.1 Introduction 577

10.1.2 Chalcogen-oxides 577
10.1.3 Chalcogen-onium Ylides 579
10.1.4 Chalcogen-onium Imides 580
10.1.5 Chalcogen-onium Salts 581
10.1.6 Chalcogenic Acids 582
10.1.7 Chalcogenate Esters 584
10.1.8 Chalcogeninamides 585
10.1.9 Chalcogen-oximines 586
10.1.10 Chalcogenuranes 586
10.1.11 Dichalcogenides 589
10.1.12 Conclusions 589
References 589

Chapter 10.2 1,1-Dithiolato Ligands and Related Selenium and

Tellurium Compounds 593
Ionel Haiduc

10.2.1 Introduction 593

10.2.2 Phosphor-1,1-dithiolates 593
10.2.2.1 Dithiophosphates (Dithiophosphoric
Acid Diesters) 596
10.2.2.2 Dithiophosphoric Acid O-monoesters
(RO)P(O)(SH)2 599
10.2.2.3 Dithiophosphinates 599
10.2.2.4 Dithiophosphonates (Dithiophosphonic
Acid O-monothioesters) 604
Contents xix
10.2.3 Arsen-1,1-dithiolates 606
10.2.3.1 Dithioarsenates 606
10.2.3.2 Dithioarsinates 606
10.2.4 Xanthates (Dithiocarbonic Acid O-monoesters) 607
10.2.5 Dithiocarboxylates 611
10.2.6 Dithiocarbamates 613
10.2.7 Dithiocarbimates and Related Compounds 617
10.2.8 Silane-1,1-dithiolates and Tin Analogs 618
10.2.9 Phosphor-1,1-diselenolates 619
10.2.9.1 Diselenophosphates 619
10.2.9.2 Diselenophosphinates 621
10.2.9.3 Diselenophosphonates 621
10.2.10 Arsen-1,1-diselenolates (Diselenoarsinates) 621
10.2.11 Tellurium Analogs 622
References 622

Chapter 10.3 Hypervalent Chalcogen Compounds 644

Waro Nakanishi

10.3.1 Introduction 644

10.3.2 Bond Distances in Hypervalent Region 645
10.3.3 Factors to Stabilize Hypervalent Bonds 646
10.3.4 Hypervalent Chalcogen Compounds 647
10.3.4.1 10–E–3 (T-shaped) 647
10.3.4.2 10–E–4 651
10.3.4.3 10–E–5 and 12–E–5 653
10.3.4.4 12–E–6 654
10.3.4.5 Higher Coordinated Species 654
10.3.5 Weak Hypervalent Interactions 655
10.3.6 Extended Hypervalent Bonds; mc–ne (m Z 4) 657
10.3.6.1 3c–4e to mc-ne (m Z 4) 657
10.3.6.2 4c–6e 658
10.3.6.3 5c–6e 661
10.3.6.4 Higher Extended Hypervalent Bonds 661
References 662

BIOLOGICAL CHEMISTRY

Chapter 11.1 Chalcogens (S, Se, Te) in Microorganisms and Plants 671
Thomas G. Chasteen and Ronald Bentley

11.1.1 Introduction 671

11.1.2 Sulfur 671
11.1.2.1 General and Secondary Metabolism.
Role of Chirality at Sulfur 671
xx Contents
11.1.2.2 Overview of Structural Types for
Sulfur-Containing Secondary
Metabolites 672
11.1.2.3 Sulfur-Containing Fungal Metabolites 674
11.1.2.4 Flavor Compounds Containing Sulfur 679
11.1.2.5 Aroma and Medicinal Roles of Sulfur-
Containing Plant Metabolites 685
11.1.2.6 Role of Plants and Microorganisms in
Production of VOSCs 692
11.1.2.7 Miscellaneous Sulfur Compounds 693
11.1.3 Selenium 695
11.1.3.1 General Biological Role of Selenium 695
11.1.3.2 Se-Containing Amino Acids 697
11.1.3.3 Selenocysteine Containing Se-Proteins 698
11.1.3.4 Manipulation of Bacterial Genes
Involving Se Resistance 699
11.1.3.5 Oxidation/Reduction Processes
Involving Selenium 700
11.1.3.6 Analytical Methods for Elemental Se
and Organo-Selenium 700
11.1.4 Tellurium 702
11.1.4.1 General Biological Role of Tellurium 702
11.1.4.2 Manipulation of Bacterial Genes
Involving Te Resistance 703
11.1.4.3 Oxidation/Reduction Processes 703
11.1.4.4 Analytical Methods for Elemental
Te and Organo-Tellurium 704
11.1.5 Summary 705
References 705

Chapter 11.2 Metal-Sulfur Clusters as the Model for the Active Sites of
Metalloenzymes 714
Yasushi Mizobe

11.2.1 Introduction 714

11.2.2 Well-Defined Metal-Sulfur Clusters in
Metalloenzymes and Syntheses of Their
Structural Models 716
11.2.2.1 Preparation and Reactions of the
FeMo Cofactor Model Clusters 716
11.2.2.2 Preparation of PN-Cluster Models 719
11.2.3 Metal-Sulfur Clusters as the Functional Models
for Metalloenzymes 721
11.2.3.1 Preparation of Metal-Sulfur Clusters
from Dinuclear Precursors 722
Contents xxi
11.2.3.2 Preparation of Metal-Sulfur Clusters
from Trinuclear Precursors 724
11.2.4 Conclusion 726
References 727

MATERIAL CHEMISTRY

Chapter 12.1 Stable Chalcogen Radicals 733

Jeremy M. Rawson and Antonio Alberola

12.1.1 Introduction 733

12.1.2 Five-Membered C/N/S and C/N/Se Rings 734
12.1.2.1 1,2,3,5-Dithiadiazolyl Radicals 737
12.1.2.2 1,3,2,4-Dithiadiazolyl Radicals 743
12.1.2.3 1,3,2-Dithiazolyl Radicals 744
12.1.2.4 1,2,3-Dithiazolyl Radicals 753
12.1.2.5 1,2,3-Trithiolium Radicals 755
12.1.2.6 1,2,3,4-Trithiazolylium Cations 757
12.1.3 Conclusions 758
References 758

Chapter 12.2 Chalcogen-Rich Compounds as Electron Donors 763

Thomas D. Westgate and Peter J. Skabara

12.2.1 Introduction 763

12.2.2 Structural Diversity 766
12.2.2.1 Molecular 766
12.2.2.2 Macromolecular 768
12.2.2.3 Polymeric 771
12.2.3 The Role of the Chalcogen 773
12.2.3.1 Heterocyclic Structure 774
12.2.3.2 Chemical Sensors: A Case Study of
Chalcogen-Metal Bonding in
Electroactive Materials 779
12.2.3.3 Use of the Chalcogens Heavier than S 784
References 790

Chapter 12.3 1,2-Dithiolene Ligands and Related Selenium and

Tellurium Compounds 797
Massimiliano Arca and M. Carla Aragoni

12.3.1 Introduction 799

12.3.2 Nomenclature 802
xxii Contents
12.3.3 Synthesis 803
12.3.3.1 Synthesis of 1,2-Dichalcogenolene
Ligands or Precursors 803
12.3.3.2 Synthesis of 1,2-Dichalcogenolene
Complexes 806
12.3.4 General Structural Features of 1,2-Dichalcogen-
olene Complexes 809
12.3.5 Applications and Properties of 1,2-Dichalcogen-
olene Complexes 810
12.3.5.1 Electrical Properties 811
12.3.5.2 Magnetic Properties 812
12.3.5.3 Optical Properties 813
12.3.6 Conclusions 816
Acknowledgements 817
References 817

SUPRAMOLECULAR CHEMISTRY

Chapter 13 Chalcogen-Halogen Secondary Bonds in Self-Assembling of

Supramolecular Structures 833
Wolf-Walther du Mont and Cristian George Hrib

13.1 General Aspects of Supramolecular Chemistry with

Soft-Soft Interactions 833
13.2 Supramolecular Aspects of Structures from Classes
of Compounds discussed in Previous Chapters 834
13.2.1 Binary Chalcogen Halides 834
13.2.2 Di- and Multichalcogen Cationic Species 835
13.2.3 Chalcogens as Donor Atoms in Molecular
Adducts 837
13.3 Supramolecular Aspects of Structures from
Lowvalent and Divalent Chalcogen-Halogen
Compounds 846
13.3.1 Association of Sulfenyl, Selenenyl and
Tellurenyl Halides 846
13.3.2 Oxidative Halogen Addition to Chalcogen-
ocarbonyl Functions R2C=Y and to
Phosphine Selenides R3P=Se 850
13.3.3 Complexes of Chalcogen Donors with
Organotellurium Electrophiles 854
13.3.4 Intermolecular Interactions in Tellurium(II)
Halide Complexes with S or Se
Donors 856
13.4 Supramolecular Aspects of Structures from
Tetravalent Chalcogen-Halogen Compounds 859
Contents xxiii
13.4.1 Cation-Anion Interactions Involving
Selenonium and Telluronium Salts 859
13.4.2 Some new Supramolecular Aspects of
Diorganylselenium and -tellurium Dihalide
Structures 860
13.4.3 The Role of Cations for Aryltetrahalogen-
otellurate(IV) Structures 862
13.5 Base Pair-Like Chalcogen-Halogen Arrays 865
13.5.1 Intermolecular Donor-Acceptor Interactions
in Solid Iodophosphine Selenides 865
13.6 Conclusion 867
References 867

Subject Index 873

CHAPTER 1

Compounds Containing the

Boron–Chalcogen B–E
(E¼S, Se, Te) Bond
MICHAEL A. BECKETT

School of Chemistry, University of Wales, Bangor, LL57 2UW, UK

1.1 Introduction
This chapter focusses on compounds with chalcogen (E¼S, Se, Te) to B bonds
and reviews the chemical literature over the period 1990–2004. Although every
effort has been made to include all important advances in all sections, the
review is not claimed to be comprehensive. The literature has been surveyed
principally by independent keyword searches of the primary chemical journals
and ISI Web of Science augmented by ACS Chemical Abstracts and RSC
Annual Reports on the Progress of chemistry, Section A (Inorganic Chemistry).
The review is structured so that relevant books, conference proceedings, and
review articles that have appeared over the period are described first, and then
the chemistry of specific topics are explored in more detail. Polyhedral boron
hydride cluster species forms a major section of this review and this section is
conveniently divided into sub-sections depending upon the nature of the B–E
linkages. The remaining principal sections of this review cover two other
important themes: heterocycles containing B–E linkages, and thioborate and
selenoborate chemistry. The review concludes with a miscellaneous section,
which includes B–E reagents.

1.2 Books and Review Articles

Sections relating to compounds with B–E bonds can be found in the author-
itative review chapters found in Comprehensive Organometallic Chemistry II
(vol 1); these chapters generally survey the literature over the period 1982–1994.
In particular, Chapter 4 has a section reporting on cyclic systems with B–E
1
2 Chapter 1
1
(E¼S, Se) bonds, and Chapter 7 surveys main group heteroboranes, with a
section on thiaboranes and their metal complexes.2 Metalloboranes, car-
boranes, and metallocarboranes are reviewed in Chapters 8, 6, and 9, respec-
tively, with many such clusters containing exo B–E bonds.3–5 The ‘International
Meeting on Boron Chemistry’ (IMEBORON) has met on a number of occa-
sions over the review period and the proceedings of these conferences have been
published; these collections give an interesting perspective on the development
of boron chemistry in general but with many relevant articles.6 A review on
chalcogenoboron hydrides was published in 1997 giving a historical viewpoint
and covering the literature to 1997.7 An overview of heteroboranes in which p-
block elements (including S, Se, and Te) have replaced one or more vertices in
parent borane cages was reported in 2002.8 The topic of thioborate and
selenoborates have been reviewed on a number of occasions,9–11 with the most
recent12 in 2003 discussing their diverse structures, which range from rings,
through clusters to 3d networks.

1.3 Polyhedral Boron Hydride Derivatives

1.3.1 Species with Exo B–Chalcogen Bonds
1.3.1.1 Boranes and Heteroboranes
There were a considerable number of reports over the period 1990–2004 on
polyhedral boron hydride species with exo-chalcogen bonds and the following
section is structured in terms of increasing polyhedral size. There were also a
few reports on polyhedral carborane species, which are at the end of this
section, but there were no reports on other heteroborane species with exo-
chalcogen bonds.
Na[H3B-m2-S(B2H5)] was obtained from reaction of NaSH with BH3.thf,13
and Na2[H3BSe2BH3], produced by the reaction of elemental Se with Na[BH4],
was found to react with excess B2H6 to form the related salt Na[H3B-m2-
Se(B2H5)].14 Bi-functional thiols (HSRSH, R¼CH2, CH2CH2, CH2CH2CH2,
1,2-C6H4) were found to react with B4H10 to afford trans-annularly bridged
species e.g. cis- and trans-[(BH2)(m2-SRS)(BH)(B2H5)]. Upon cooling a fully
reversible rearrangement occurred and a ‘butterfly’-type structure, [(BH2)(m2-
SRS)(B3H6)] was obtained, again as a mixture of cis and trans isomers.15 The
adduct, B3H7(SMe2) (1) which was isolated as a liquid at room temperature,
reacted slowly with additional SMe2 to yield B5H9 with the mechanism of this
borane framework expansion believed to involve the diborane(4) adduct,
B2H4(SMe2)2.16 The reaction of 1 with excess NMe3 in Me2S at low temper-
ature (
80–
30 1C) led to B2H4(NMe3)2, but the ligand-exchanged adduct
B3H7(NMe3) was shown not to be an intermediate in this reaction.17 Treatment
of 1 with BCl3 yielded the chloro-substituted derivative B3H6Cl(SMe2).18
Reactions of B5H11 and Me2S produced B4H8(SMe2) (2) and an unstable
pentaborane adduct, B5H11(SMe2), which was shown to be a precursor to the
Compounds Containing the Boron–Chalcogen Bond 3
19 2

tetraborane adduct, 2. The closo anion [B6H6] was found to react with
(SeCN)2 in organic media to produce [PPh4]2[(SeCN)B6H5], characterized by
single-crystal X-ray diffraction (XRD) studies.20 Treatment of [NBu4][B6H7]
with (SCN)2 or (SeCN)2 in dichloromethane solution in the presence of solid
KOH resulted in the hexaborate species [NBu4]2[B6(ECN)6] (E¼S, Se).21 The
conventional preparation of 4-(L)-arachno-B9H13 derivatives, by ligand ex-
change on 4-(SMe2)-arachno-B9H13, was shown by NMR spectroscopy to also
generate the previously unreported isomeric species 5-(L)-arachno-B9H13.22
A series of mono- and di-substituted Me2S derivatives were obtained from
the reaction of DMSO in acid with Cs2[B10H10], and through a modified
procedure the tri-substituted 1,10-(Me2S)2-2-(MeS)B10H7 species was ob-
tained.23 The closo anion [B10H10]2
was found to react with (SeCN)2 in
organic media and produced [PPh4]2[(SeCN)B10H9] characterized by single-
crystal XRD studies.20
The hydroboration of alkenes with 6,9-(SMe2)2B10H12 (3) yielded 6-R-8-
(SMe2)-B10H11 (R¼Prn, octn, hexn, 3-methyl-2-butyl, 2,3-dimethyl-2-butyl),
which was converted to the corresponding alkyl derivative, 6-R-B10H13, by
treatment with ‘super-hydride’ (LiEt3BH/thf).24 Mechanistic experiments on the
formation of 3 from nido-B10H14 and its subsequent reaction with 2,3-dime-
thylbut-2-ene to form nido-5-(Me2S)-9-(CMe2CHMe2)B10H11 indicated that the
movement of the Me2S from B6 to B5 did not involve a concerted rearrange-
ment of the boron cage, but rather a migration of H and Me2S on an otherwise
static borane cluster.25 A high yield route to nido-6-alkyl decarborane(14)
derivatives starting from 3 via a one-pot synthesis was reported with XRD
results described for nido-6-(CMe2CHMe2)-8-(SMe2)B10H11 (Scheme 1).26

Me2S H H SMe2
H

3
Scheme 1

Compound 3 reacted with the phosphaalkyne PCtBu to form a product with

two B10 cages linked by a HPCBut bridge, [B10H11(SMe2)][CButPH][B10H12].27
The mild thermolysis of 3 in inert hydrocarbon solvents gave the tridecaboranyl
species, 6,9-(Me2S)2-arachno-B10H10-1,5-(6 0 -nido-B10H13)2 (4) in 23% yield
(Figure 1).28 The reaction of Me2Se2 with nido-B10H14 yielded arachno-6,7-m-
(MeSe)B10H13, whereas Me2S2 failed to react under similar conditions; how-
ever, the analogous thiomethyl derivative, 6,7-m-(MeS)B10H13, was formed by
the reaction of nido-B10H14 with Me2S3.29 The kinetics of ortho-C2B10H12
formation from acetylenes (propargyl bromide, but-2-yne-1,4-diacetate, or
non-1-yne) and arachno-6,9-B10H12L2 [L¼Me2S (3), Ph2S, But2S, (C6F5)2S,
4 Chapter 1

Figure 1 Molecular structure of 6,9-(SMe2)2-arachno-B10H10-1,5-(6 0 -nido-

B10H13)2 (4)
(Reproduced with permission from Chem. Commun., 2001, 1788.)

MePhS, Me(C6F5)S, or MeButS] have been investigated in detail: the rate

constants decreased both with increased electronegativity and/or increased size
of the substituent on S, with the yield increased as the size and/or basicity of the
Lewis base increased.30
Excess H2SO4 and Me2S were found to react with [Me3NH][B11H14] to yield
7-(SMe2)-B11H13 in good yield; upon warming to 110 1C, the adduct rearranged
to a mixture of 1- and 7-isomers.31
A one-step preparation of the Me2S-substituted icosahedral boranes 1,7-
(SMe2)2B12H10 (5), 1,12-(SMe2)2B12H10 (6), and [SMe3][B12H11(SMe2)] has
been reported from the self-condensation reaction of BH3.SMe2.32 The 1,2-
isomer, 1,2-(Me2S)2B12H10 (7) obtained from a mixture of products from the
pyrolysis of BH3.SMe2 was characterized by XRD and multinuclear NMR, and
Compounds Containing the Boron–Chalcogen Bond 5
its spectral characteristics were compared with earlier reported 5 and 6 deriv-
atives (Scheme 2).33 The reaction of [PdCl2(SMe2)2] with Li2[B12H12] at room
temperature also resulted in 5 and 6.34 Two series of compounds 9-X-1,7-
(Me2S)2B12H9 and 9,10-X2-1,7-(Me2S)2B12H8 (X¼Cl, Br, I) have been prepared
from 5 with various halogenating reagents, and the reaction of 5 with PhSeBr
and 2,4-(NO2)2C6H3SCl afforded 9,10-(PhSe)2-1,7-(Me2S)2B12H8 and 9-{2,4-
(NO2)2C6H3S}-1,7-(Me2S)2B12H9, respectively.35 The reaction of potassium
phthalimide in DMF, or NaSEt in EtOH/CH3CN, with either the 5, 6, or 7
produced the corresponding isomers of the anion [(MeS)(Me2S)B12H10]
; if
excess nucleophile was used, then the dianion [(MeS)2B12H10]2
was pro-
duced.36 The anions [(Me2S)B12H11]
and [(MeS)B12H11]2
and 5, 6, and 7
were reduced by excess lithium in methylamine at
15 1C to [(HS)B12H11]2

and the dithiols, [(HS)2B12H10]2
.37 A variety of S-alkylated products were
obtained from alkylation of the methylthioethers [(MeS)B12H11]2
, [1-(MeS)-2-
(or 7 or 12)-(Me2S)B12H10]
, and [1,2-(or 7,12)-(MeS)2B12H10]2
.38
[PPh4]2[(ECN)B12H11] (E¼S, Se) have been reported20,39 with the sulfur com-
pound characterized by XRD.

SMe2 SMe2 SMe2

SMe2

SMe2

SMe2
5 6 7
Scheme 2

The regiospecific cluster degradation of closo-1,2-C2B10H12 in the presence of

SMe2 proceeded via the nido-[7,9-C2B10H13]
intermediate and afforded exo-6-
(SMe2)-arachno-4-CB8H12.40 The synthesis and characterization of a three
carborane derivatives, 10-(SEtPh)-7,8-C2B9H11, 7-Me-10-(SMe2)-7,8-
C2B9H10, 7-Me-10-(SEt2)-7,8-C2B9H10, along with enhanced characterization
of some related compounds e.g. 10-(SR2)-7,8-C2B9H11 (R2¼Me2, Et2, {CH2}4)
have been reported.41

1.3.1.2 Metalloboranes and Metalloheteroboranes

In constrast to the previous section, the literature in this area over the period
of the review was dominated by metalloheteroborane (mainly metallocar-
borane) chemistry, narrowly focussed on ‘charge-compensated’ carbollide
{C2B9H10L}
derivatives, with relatively few examples of metalloboranes. In
6 Chapter 1
these charge-compensated derivatives, the nido 11-vertex {C2B9} carbollide (1-)
anion is coordinated Z5 to a metal centre and in the process forms an
icosahedral closo 12-vertex {MC2B9} cluster.

− −
SMe2 SMe2
C
C C C

8 9
Scheme 3

The chemistry of monoanionic carborane ligands has been investigated by

exploring the conformation adopted by formal two-orbital metal cluster bond-
ing contributors by reactions of Tl[9-(SMe2)-nido-7,8-C2B9H10] (Tl8) with com-
plexes of Rh(I) and Pd(II).42 The synthesis and structure of the ferracarborane
Fe82 and its charge transfer salt with 2,3-dichloro-5,6-dicyano-p-benzo-
quinone (9) has been reported with its magnetic properties discussed
(Scheme 3).43 The mixed-sandwich ferracarborane complex CpFe8 has been
synthesized and characterized by cyclic voltametry, IR, and 1H and 11B NMR
spectroscopy; it formed stable 1:1 charge transfer salts with 9 and 7,7,8,8-
tetracyano-2,3,5,6-tetrafluoroquinodimethane.44 The complex [(cod)Rh8] has
been used to prepare the halide complexes [{X2Rh8}2] (X¼Cl, Br, I) by reaction
with HX.45 These complexes have been further used to prepare several sandwich
and half-sandwich complexes containing the ‘Rh8’ fragment.45 The reaction of 8
with [{(arene)RuCl2}2] (arene¼C6H6, 1,3,5-C6H3Me3) afforded the cationic
ruthenium arene cluster complexes [(arene)Ru8][BF4].46 Reaction of
[{RuCl2(C6H6)}2] with [10-(Me2S)-7,8-nido-C2B9H10]
(10) afforded the ex-
pected cationic complex [(C6H6)Ru10]1 and the unexpected neutral complex
[(C6H6)Ru{10-(HS)-7,8-nido-C2B9H10}].47 Ruthenacarborane clusters of
the formula [3,3,3-H(PPh3)2-8-L-closo-3,1,2-RuC2B9H10] (L¼SMe2, SEt2,
S(CH2)4, SEtPh) and [1-Me-3,3,3-H(PPh3)2-8-L-closo-3,1,2-RuC2B9H9]
(L¼SMe2, SEt2) were prepared by the reaction of the corresponding ligands
with [RuCl2(PPh3)3].48 A series of {(PPh3)2Rh(I)} fragment half-sandwich com-
plexes were similarly prepared by reaction of these charge-compensated ligands
with [RhCl(PPh3)3].49 Ruthenium complexes with monoanionic carborane lig-
ands e.g. [RuH(PPh3)38], [RuH(PPh3)3{9-(SR2)-7-Me-7,8-C2B9H9}], have been
shown to efficiently catalyze the Kharasch addition of CCl4 across olefins.50 The
cluster substitution product, [Mo(CO)2(Z3-C3H5){(7,8-Me2-7,8-C2B9H8-10-
(SMe2)}], was obtained from treatment of the salt [NEt4][Mo(CO)2(Z3-
C3H5)(7,8-Me2-7,8-C2B9H9)] with [CPh3][BF4] and SMe2 in CH2Cl2.51 Three
dialkylsulfane-substituted nido carboranes 7,8-Ph2-10-(SR2)-7,8-nido-C2B9H10
Compounds Containing the Boron–Chalcogen Bond 7
(R2¼Me2, Me/Et, Et2) have been synthesized and characterized and the
SMe2-labelled B atoms gave useful stereochemical information on the course
of 12-vertex MC2B9 isomerizations.52 The synthesis and reactivity of the steric-
ally encumbered charge-compensated carborane 7-Ph-11-(SMe2)-nido-C2B9H10
and its conversion to [1-Ph-3,3-(CO)2-7-(SMe2)-3,1,2-closo-RhC2B9H8] has been
described.53
The donor molecule Me2S reacted with the anion [Fe(CO)3(Z5-7-CB10H11)]

in the presence of acids and hydride-abstracting reagents and gave the zwit-
terionic complex [Fe(CO)3(Z5-9-(SMe2)-7-CB10H11)] in which the SMe2 was
bound to a B atom lying in a b site with respect to the C.54 Reaction of the
monocarborane derivative [Pt2(PEt3)4(Z5:Z5-9,9-I(H)-7-CB10H10)2] with
PhSeCl, Ph2Se2, and PhTeI yielded products with chalcogen substituents on
Pt, or Pt and B.55
The electronically saturated chromaborane [Cp*2Cr2B4H8], when reacted
with CS2, produced in high yield the saturated cluster [Cp*2Cr2(CH2S2)B4H6]
(11), which contained the intracluster bridging methanedithiolato {CH2S2}
ligand (Figure 2).56 The reaction of CS2 with the open nido-6-iridadecaboranes
[H(PPh3)2-nido-6-IrB9H13] and
yielded closo 10-vertex species with boron to metal dithioformate bridges.57
The isocloso species re-
acted similarly and produced the closo species [10-(PPh3)-2,6:2,9-(m-S2CH2)2-2-
( with an unusual isocloso - closo
conversion.57

Figure 2 Molecular structure of [Cp*2Cr2(CH2S2)B4H6] (11)

(Reproduced with permission from Organometallics, 1996, 15, 1964.)
8 Chapter 1

1.3.2 Species with Chalcogen Atoms within the Cage

1.3.2.1 Chalcogenoboranes
This important area of boron–chalcogen chemistry has made some tremendous
advances, particulary in macropolyhedral systems, in recent years. The topic
was recently reviewed7,8 in 1997 and 2002. This section is again ordered in
increasing numbers of boron atoms within the cage.
A series of exo-6-(L)-arachno-4-SB8H10 adducts (L¼SMe2 (12) PPh3, MeCN,
NMe3, py, urotropine, MeNC, quin) have been prepared from arachno-4-
SB8H12 (13) and the corresponding Lewis bases with the X-ray structures of
three representative examples (L¼urotropine, 1/2urotropine, MeNC) reported
(Scheme 4).58 The thianonaborane anion nido-[9-SB8H9]
was prepared by
deprotonation of 12 with Na metal or NaH; the reaction was reversed by
treatment of the product with Me2S and CF3COOH.59 Thermolysis of 13 in
cyclohexane generated the 18-vertex macropolyhedral anti-9,9 0 -S2B16H16 (14)
in modest yield,60 and mild thermolysis of 12 resulted in the formation of the
macropolyhedral S2B17H17(SMe2) (15) in low yield.61 The structure of 15 is a
conventional nido-type 11-vertex {SB10H9} sub-cluster fused to an arachno-type
10-vertex {SB9H8(SMe2)} sub-cluster with two boron atoms in common.61
S
S H
H S H
H H
H

13 16 17
Scheme 4

The microwave spectrum of 1-SB9H9 has been reported together with high-
level ab initio and DFT calculations.62 The reactions of nido-6-SB9H11 (16) with
imines and trimethylsilylazide have been investigated; the latter reagent gave the
first examples of a new class of fused-ring cluster triazene-thiaborane, (m2-(4,exo-
9)-1-SiMe3-3-H-N3)-arachno-6-SB9H10, in 42% yield.63 N-tbutylformaldimine
gave a unique zwitterionic compound, 9-(ButNH2CH2)-nido-6-SB9H9, which
formed an adduct upon treatment with CH3CN.64 Reactions between 16 and
Lewis bases (L) gave a series of corresponding arachno compounds, exo-9-(L)-
arachno-6-SB9H11 (L¼NEt3, quinoline, isoquinoline, urotropine, py, MeCN,
MeNC, NH3, SMe2, PPh3).65 The compound arachno-9-(PPh3)-6-SB9H11 was
obtained upon thermolytic decomposition of arachno-[exo-9-{Cl-trans,cis-
(PPh3)2H2Ir}-6-SB9H11].66 The crystal structure of 9-(PCy2Ph)-6-SB9H11 has been
determined and the cluster had the expected arachno 10-vertex {SB9} geometry
with the phosphine substituent exo.67 The structure of Cs[6-SB9H12] has been
established by XRD studies.66 Dehydrogenation of arachno-2-H-2,3-S2B9H10
Compounds Containing the Boron–Chalcogen Bond 9
68
afforded the previously reported nido-7,9-S2B9H9. The structure of nido-
Se2B9H9 has been unambiguously determined as the 7,9-isomer using high-field
11
B NMR69 and results from MNDO MO calculations of the S2B9H9 thiaborane
analogue have shown that all the 2c/2e bonds were localized around the {B3S2}
open face. The arachno dithiaborane cluster anion [2,3-S2B9H10]
was obtained
from the reaction of nido-[6-SB9H10]
anion with S8, and reactions of this
dithiaborane with MeI, CH2I2, and H2SO4 have been reported.68 The nido
11-vertex thiaboranes [7-SB10H11]
and 7-SB10H12 were produced by synthetic
sequences involving the reaction of SCl2 with B10H14 followed by in situ dehy-
drohalogenation initiated by ‘proton-sponge’.70
The UV–PES spectra of the thiaborane nido-7-SB10H12 has been reported
and compared with spectra from more open thiacarboranes.71 The previously
known nido-[7-SB10H11]
anion was obtained in 45% yield from the reaction of
S8 with a solution of anti-[B18H20]2
.72
The molecular structure of the closo 12-vertex 1-SB11H11 cluster (17) has
been studied by electron diffraction methods augmented by ab initio calcula-
tions. Substantial distortions away from the regular icosahedron occurred by
expansion of the pentagonal belt adjacent to sulfur.73 The UV–PES spectra of
17 has also been reported,71 and its microwave spectrum has been investigated
and demonstrated that the molecule had C5v symmetry.74
The18-vertex non-metallated adduct S2B16H14(PPh3) was a coproduct in the
reaction of [NiBr2(PPh3)2] with 14.75,76
The reaction of metabisulfite with syn-B18H22 gave a good yield of the
macropolyhedral thiaborane anion [SB17H19]
, which exhibited an arachno–
nido two-borons-in-common cluster-fusion mode.77 The reaction of S8 on a
solution of anti-[B18H20]2
gave as the major product the macropolyhedral
anion [S2B17H18]
(18), isolated in 48% yield as its [PPh4]1 salt and charac-
terized crystallographically.72 The cluster structures of the macropolyhedral
thiaborane 15 and thiaborane anion [S2B18H19]
were investigated at the
B3LYP/6-311 and G**//B3LYP/6-31G* density functional theory level.78
The treatment of 18 with oxidizing acids quantitatively yielded S2B17H17
characterized as its anion [S2B17H16]
.79
The double-cluster anion [S2B18H19] (19) (Figure 3) was prepared from the
interaction of S8 with [syn-B18H21]
.80

1.3.2.2 Metallochalcogenoboranes
A series of new arachno and hypho metalladithiaborane clusters have been
generated from the hypho-[S2B6H9]
anion (20): reactions with [{(C6Me6)R-
uCl2}2], [Cp*Co(CO)L], [(dppe)NiCl2], and [(PMe3)2Rh(CO)Cl] have been
reported and products, including hypho-[1,1-(C6Me6)Cl-1,2,5-RuS2B6H9] and
arachno-[7-(C6Me6)-7,6,8-RuS2B6H8], were characterized by XRD studies.81 A
dimeric product [{Pd(PPh3)(S2B6H8)}2] was obtained from the attempted re-
crystallization of a product obtained from the reaction of [PdCl2(PMe2Ph)2]
10 Chapter 1

Figure 3 Crystallographically determined structure of the anion [S2B18H19]
(19)

(Reproduced with permission from J. Chem. Soc., Dalton Trans., 1998,
2965.)

with 20.82 The molecular structure of the open 9-vertex cluster arachno [5,5-
(PMe2Ph)2-4,6,5-S2PdB6H8] has been established.83
The synthesis, X-ray structure, and dynamic NMR properties of the arachno
10-vertex cluster [9,9-(PMe2Ph)2-9,6,8-PtS2B7H7] has been reported; the com-
pound was fluxional via a vertex flip of the {Pt(PMe2Ph)2} moiety.84
The formation of 9-, 10-, and 11-vertex metallathiaborane clusters, by
insertion of the S atom into existing metalloborane frameworks, has been
achieved for clusters containing eight boron atoms. Thus, the reaction of
arachno-[(PMe3)2(CO)HIrB8H12] with H2S yielded nido-[2,2,2-(PMe3)2H-2,6-
IrSB8H10], closo-[2,2,2-(PMe3)2H-2,1-IrSB8H8, and nido-[(PMe3)(CO)-
HIrS2B8H8].85 The reaction of [RhCl(PPh3)3] with arachno-[S2B9H10]
(21)
yielded nido-[(PPh3)2HRhS2B8H8],86 while [{(C6Me6)RuCl2}2] reacted with
arachno-[6-SB9H12]
(22) to yield closo-[2-(C6Me6)-2,1-RuSB8H8].87 The
platinathiaborane species [(PMe2Ph)2PtSB8H12] was obtained from [PtMe2(P-
Me2Ph)2] with 13.88
Reaction of [{(p-cymene)RuCl2}2] with 22 yielded closo-[2,3-(p-cymene)2-
2,3,1-Ru2SB9H9] and [2,3-(p-cymene)2-2,3,1-Ru2SB9H8Cl-7], and the open nido
species [7-(p-cymene)-7,8-RuSB9H10Cl-11].87 The reaction of 16 with
[{IrCp*Cl2}2] yielded nido-[8-Cp*-8,7-IrSB9H11], whereas reaction with 22
yielded a mixture of products e.g. nido-[8-Cp*-8,7-IrSB9H10-Cl-9], nido-[8-
Cp*-8,7-IrSB9H10-Cl-10], and closo-[1-Cp*-1,2-IrSB9H9].66 The structure of
nido-[8-Cp*-8,7-IrSB9H10Cl-9] was established by XRD studies.66 Cs[6-
SB9H12] reacted with Vaska’s compound to afford arachno-[exo-9-{Cl-trans,-
cis-(PPh3)2H2Ir}-6-SB9H11]66 and with [Rh(PPh3)3Cl] at room temperature in
ethanol solution to produce the orange air-stable compound [8,8-(PPh3)2Cl-
8,7-RhSB9H10] in high yield.89 This cluster’s nido 11-vertex cage geometry was
established by XRD studies and in solution it exhibited a fluxionality involving
swinging the metal–ligand fragment from one side to the other of the {SB9}
Compounds Containing the Boron–Chalcogen Bond 11
89
heteroborane cage. The nido species [8,8,8-(PMe2Ph)3-8,7-RhSB9H10] was
prepared in good yield by the addition of excess PMe2Ph to [8,8-(PPh3)2-8,7-
RhSB9H10]90, and this crystal structure compared to that of [8,8-(PPh3)2-9-
(EtO)-8,7-RhSB9H9].0.95CH2Cl2 showed that the addition of a third exo ligand
on Rh had minimal effect on the cluster geometry.91 The reaction of [8,8-
(PPh3)2-8,7-RhSB9H10] with CO resulted in [8,8,8-(CO)(PPh3)2-8,7-RhSB9H10]
in quantitative yield and thermolysis of this nido species afforded a closed 11-
vertex cluster [1,1,3-(CO)(PPh3)2-closo-1,2-RhSB9H8] in 46% yield.92 The syn-
thesis and solid-state structure of nido-[8,8-(dppe)-8,7-RhSB9H10].2CH2Cl2 has
been reported. This 11-vertex {RhSB9} polyhedron showed a gross nido
icosahedral geometry while apparently possessing a cluster count more appro-
priate to a closo geometry; two one-electron agostic-type Rh–H–C interactions
were proposed as a source of the additional electron pair.93,94 Two new
isoelectronic nido species [m-9,10-(SMe)-8,8-(PPh3)2-8,7-IrSB9H9] and [m-9,10-
(SMe)-8-(Z4-Cp*H)-8,7-IrSB9H9] have been characterized by XRD studies.95
The reactions of the unsaturated cluster [8,8-(PPh3)2-nido-8,7-RhSB9H10] with
bidentate phosphine ligands (dppm, dppe, dppp) have been studied and sub-
stitution of the two PPh3 ligands occurred to give the related bidentate
complexes and/or clusters with the bidentate phosphines ligands bridging.96,97
The cluster [8,8-(Z2-dppm)-8-(Z1-dppm)-nido-8,7-RhSB9H10] (23), containing a
pendant PPh2 group, reacted with BH3.thf and gave the species [8,8-(Z2-
dppm.BH3)-nido-8,7-RhSB9H10] with a bidentate dppm.BH3 ligand.98 Com-
pound 23 also reacted with [{MCp*Cl2}2] (M¼Rh, Ir) and gave bimetallic
species.99,100 The metal reagent [RhCl(PPh)3] inserted into the quadrilateral
face of the isonido 11-vertex cluster [1-(PPh3)-1,3-(m-dppm)-isonido-1,2-
RhSB9H8] and yielded the icosahedral product [2,2,3-(PPh3)Cl2-2,3-(m-Cl)-
3,7-(m-dppm)-closo-2,3,1-Rh2SB9H8].101 Reactions with [MCl(PPh3)3] (M¼Rh,
Ir) with 21 yielded nido-[(PPh3)2HIrS2B9H9] and nido-[(PPh3)2RhSB9H11].86
A series of closed polyhedra {EMB10} ((E¼S, Se, or Te; M¼Rh, Ru, Pd, Mo,
Cu, or Pt) have been reported.102–111 Nido-[7-TeB10H11]
(24) reacted with
[{RhCp*Cl2}2] in CH2Cl2 solution to give closo-[2-Cp*-1,2-TeRhB10H10] in
moderate yield, and with [{Ru(Z6-arene)Cl2}2] (arene ¼ 4-MeC6H4iPr, or C6H6)
to give closo-[2-(arene)-1,2-TeRuB10H10].102 Both clusters were structurally
characterized by XRD as closed {TeMB10} polyhedra based on a distorted
icosahedron with Te and M adjacent. The reaction of closo-[2,2,2-H(PPh3)2-
1,2-TeRhB10H10] with metal carbonyl species (e.g. [Os3H2(CO)10], [Mo(CO)6])
led to the unexpected products: closo-[(PPh3)(CO)Rh2Te2B20H20] and [{closo-
(PPh3)RhTeB10H10}2], which both contained two {RhTeB10} cages.103 The
synthesis of a series of 12-vertex closo tellura- and selenapalladaborane cluster
derivatives [2,2-(PR3)2-2,1-PdEB10H10] and [2,2-X(PPh3)-2,1-
PdTeB10H9(PPh3)] (R3 ¼ Me2Ph, MePh2, Ph3; E¼Se, Te; X¼Cl, Br, I, CN,
SCN, O2CMe) has been achieved starting from the nido-[7-EB10H11]
anions
and appropriate Pd(II) complexes, or from [2,2-I(PPh3)-2,1-
PdTeB10H9(PPh3)].104 The reaction of [2,2-I(PPh3)-2,1-PdTeB10H9(PPh3)] with
Ag[BF4] in toluene/H2O solution at room temperature led to a cationic cluster
closo-[2,2-(H2O)(PPh3)-2,1-PdTeB10H9(PPh3)][BF4] in excellent yield and from
12 Chapter 1
which many cationic clusters were obtained by displacement of the coordinated
H2O by neutral donor ligands (CO, CNtBu, CNC6H11, NCMe, thf, SC4H8).105
An alternative route to cationic clusters e.g. closo-[2,2-(PR3)2-2,1-
PdTeB10H9(PPh3)]I involved the reaction of [2,2-I(PPh3)-2,1-PdTeB10H9
(PPh3)] with excess phosphine (PR3 ¼ PMe2Ph, PMe3).106 The synthesis and
structural characterization of the rhodatelluraborane cluster closo-[2,2-
(PPh3)(PhNHCS2)-2,1-RhTeB10H10] has been reported.107 The fluxional
behaviour of {M(PR3)2} in closo 12-vertex {MZB10} (Z¼S, Se, Te) metal-
loheteroboranes has been characterized and a mechanism for the rotation of
the {M(PPh3)2} units above the heteroborane cage was suggested.108 The closo
complex [2,2,2-{Z1-SC(H)NPh}(PMe2Ph)2-2,1-RhTeB10H10] has been charac-
terized by XRD and was described as one of the first thioformamidate com-
plexes to be isolated.109 The paramagnetic B-fluorinated mixed-sandwich
compound [2-(C7H7)-7,11-F2-closo-2,1-MoTeB10H8] (25), formed from reac-
tion of 24 (Scheme 5) with [Mo(CO)3(Z7-C7H7)][BF4] had the 2{BF} units in
adjacent positions within the closo 12-vertex {MoTeB10} cluster (Figure 4); the
compound exhibited a reversible one-electron reduction at E1¼
0.39 V in
CH2Cl2 solution.110 The platinathiaborane species [(PMe2Ph)2PtSB10H10] was
obtained by reaction of [PtMe2(PMe2Ph)2] with nido-7-SB10H12.88 The icosa-
hedral closo-{CuSeB10}cage was identified in the structure of [(PPh3)2Cu2-
SeB10H10], which has Cu and Se atoms adjacent; the exo-cage Cu(PPh3) unit
was bonded to one triangular {CuB2} face via a Cu–Cu bond and two Cu–H–B
interactions.111

H -
H
Te
Rh(η2-dppm)(η1-dppm)
S

23 24
Scheme 5

The macropolyhedral compound 14 reacted with [PtMe2(PMe2Ph)2] to give

the [(PMe2Ph)2PtS2B15H14(NHCOMe)]88 and with [{RhCl2Cp*}2] yielded both
syn and anti isomers of the macropolyhedral rhodathiaboranes
[Rh2Cp*2S2B15H14(OH)]; reaction with [NiBr2(PPh3)2] in the presence of base
afforded the 19-vertex cluster [(PPh3)NiS2B16H12(PPh3)]. The latter consisted
of a nido-shaped {1-NiB8] sub-cluster and a closo-shaped {1,4-NiSB10} sub-
cluster fused with a {NiB2} triangular face in common.75,76 Reaction of syn-
[Cp*IrB18H20], obtained from [{IrCl2Cp*}2] with syn-B18H22 and base, with
elemental sulfur afforded, by direct heteroatom insertion of the 20-vertex
cluster anion, [Cp*IrSB18H19]
.112
Compounds Containing the Boron–Chalcogen Bond 13

Figure 4 View of [2-(Z7-C7H7)-7,11-F2-2,1-closo-MoTeB10H8] (25)

(Reproduced with permission from J. Chem. Soc., Dalton Trans., 2001,
1521.)

1.3.2.3 Chalcogenoheteroboranes and Their Metallo Derivatives

Chalcogenoheteroboranes and their metallo derivatives are restricted to thio
derivatives with no known examples in selena- or telluraheteroborane chemis-
try. The six-boron thiacarborane anion hypho-[7,8-CSB6H11]
(26) has been
prepared from arachno-4-CB8H14 (27).113 The first azathiaborane clusters,
hypho-7,8-NSB6H11 and arachno-6,9-NSB8H11, were prepared by the reaction
of n-butylnitrite with 13 in Et2O or nido-6-SB9H11 in C6H6.114 The transfor-
mation of 3,4-bis(isopropylidene)-2,5-dichloro-1,2,5-dithiaborolane derivatives
to the corresponding nido-4,5-diisopropyl-2,4,5-thiadicarbahexaboranes in low
yield has been reported; the nine-vertex cluster closo-5,6-Pri2-4,5,6-SC2B6H6
was also detected by GC–MS and identified by the ab initio/IGLO/NMR
method.115 A 4,5-dicarba-2-thia-nido-hexaborane was synthesized by the hy-
droboration reaction of 2,5-diduryl-1-thia-3,4-diisopropylidene-2,5-diborolane
by BH3.thf, with the product characterized by MS and multinuclear NMR
spectroscopy.116 The structure of the nine-vertex arachno-thiadicarbaborane
C2SB6H10 was established by the ab initio/IGLO/NMR method as the 4,6,8-
C2SB6H10 isomer; the method also unambiguously ruled out the 4,6,5-
C2SB6H10 structural alternative.117 The nine-vertex arachno-5-Cp*-5,4,
6-MCSB6H10 (M¼Rh, Ir) clusters were prepared from the 10-vertex
14 Chapter 1
arachno-6,9-CSB8H12 (28) (Scheme 6) or 9-vertex arachno-4,6-CSB7H11 (29) by
site-specific metal centre additions with directed elimination of specific boron
sites.118 The reaction of [{IrCl2Cp*}2] with 26 afforded [2,7-Cp*2-nido-2,7,8,6-
Ir2CSB6H8] and [2,7-Cp*2-nido-2,7,8,6-Ir2CSB6H7-9-Cl].119

H H
H S H
C C
H H H
H

27 28
Scheme 6

The seven-boron thiacarborane 29 was prepared from 28.113 The arachno

cluster [9,9-(PMe2Ph)2-9,6,8-PtCSB7H9], obtained in moderate yield from 29,
[PtCl2(PMe2Ph)2], and proton sponge, underwent ortho-cycloboronation upon
120
thermolysis to
The nine-vertex monocarborane 27 reacted with S8 in the presence of Et3N to
yield 28.121 The UV–PES spectra of the thiaboranes closo-1-SB11H11 and nido-
7-SB10H12 have been compared with spectra from more open thiacarboranes
nido-7,8,10-C2SB8H10 and 28, with the main conclusion being that there was a
significant contribution of the bridge hydrogen atoms to the cluster-bonding
HOMO and the implication that the bridge H atoms were involved in cluster
bonding.71 An extended series of thiacarborane clusters (26, 29, arachno-[6,9-
CSB8H11]
, nido-7,9-CSB9H11, and nido-[6,9-CSB8H9]
) have been prepared
from 27.113 The thiacarborane 28 reacted with [RhCl(PPh3)3] in ethanol
solution at room temperature and produced the nido species [8,8,8-H(PPh3)2-
8,9,7-RhCSB8H10] in high yield.122 The 11-vertex thiacarborane anion [1,6,
7-C2SB8H11]
, obtained from the addition of S8 to the 10-vertex [6,9-
C2B8H10]2
anion, was characterized using the ab initio/GIAO/NMR
method.123
Nido-7,9-CSB9H11 has been prepared from 28.113 A nido-11-vertex
thiacarborane, 7,10,11-SC2B8H10, and the first thiaphosphaborane, nido-10-
Ph-7,10-SPB9H9, were produced by synthetic sequences involving the reaction
of an organophosphorus dihalide and/or sulfur dihalide with borane clusters
followed by in situ dehydrohalogenation reactions initiated by ‘proton-
sponge’.70

1.4 Binary, Ternary, and Quarternary

Chalcogenoborates
Rapid progress in recent years has been made in the understanding of ternary
and quarternary chalcogenoborates due to improvements in crystallographic
Compounds Containing the Boron–Chalcogen Bond 15
and solid-state preparative methods. However, the chemistry of known chal-
cogenoborate derivatives is limited to thio- and selenaborates with no known
telluraborates. Despite this, a wide variety of compounds have been synthesized
and structurally characterized over the period of this survey. As noted in
Section 1.2, this topic has been reviewed recently.12
Two new high-pressure phases of boron sulfide, B2S3-II and B2S3-III, have
been synthesized at 3.0–6.3 GPa.124 A new method of preparing meta-thioboric
acid (c-HBS2), by reaction of H2S with B2S3 in the vapour phase, has been
reported.125 The IR spectra of a series of binary K2S/B2S3 glasses has been
reported with spectra similar to those of the corresponding sodium thioborate
system.126 The XPS spectra of vitreous and crystalline Li2S/B2S3 compounds
were obtained and analyzed by theoretical calculations.127 A structural neutron
diffraction study of Li2S/B2S3 glasses has also been reported.128 TlBS3 was
obtained as a glassy product from Tl2S.2B2S3 after treatment for 7 h at 850 1C
followed by annealing in a two-zone furnace for 400 h at 350–400 1C.129 A new
series of anhydrous protonated chalcogenide glasses, (H2S)x(B2S3)1
x, analo-
gous to alkali-modified glasses have been prepared; characterization showed
that these materials were unique and did not exhibit the borate anomaly.130
Mixing HBS2 and B2S3 and GeS2 yielded proton-containing glasses in which,
except in the GeS2-rich formulations, the borate coordination was found to be
trigonal.131
The orthothioborates Na3BS3, K3BS3, and Rb3BS3 have been prepared in
solid-state reactions of metal sulfide, amorphous boron, and sulfur at 600 1C
and their crystal structures revealed that all three compounds contained isolated
BS33
anions.132 The orthothioborates Li3BS3, Cs3BS3, Sr3(BS3)2, Li2CsBS3,
LiBaBS3, and LiSrBS3 have also been prepared and their structures, determined
by XRD studies, also contained isolated planar [BS3]3
anions.133–136 The
crystal structure of Li3BS3, obtained by crystallizing the corresponding glass,
exhibited higher symmetry than other M3B(O,S)3 structures and Li3BS3 was
described as a new member of the M3AX3 group of compounds.137
The structure of Cs2B2S4 contained isolated B2S42
groups consisting of
four-membered B2S2 rings with exocylic S atoms on each B; this was the first
reported example of edge-sharing BS3 groups in isolated thioborate anions.138
The four-membered B2S2 ring was found as a building block in the polymeric
thioborate anion structures observed for TlBS2 and SrB2S4.139 The crystal
structure of the barium metathiaborate, BaB2S4, showed the boron atoms in
both trigonal and tetrahedral coordination in a 1:1 ratio, in infinite anionic
chains140 and a new crystalline phase of EuB2S4 has been prepared and its
crystal structure revealed polymeric [(B2S4)2
]n anions.141
The synthesis, crystal structures, and properties of LiSrB3S6 and M3B3S6
(M¼Na, K, Rb) have been reported.142 The ternary thioborate Sr3(B3S6)2 and
the quarternary thioborate LiBaB3S6 both contained boron centres in trigonal
planar coordination environments with isolated B3S63
anions consisting of
six-membered B3S3 rings with three exocyclic S atoms.136,143
The perthioborate, RbBS3, and Th3B3S10 were prepared at 600 and 850 1C,
respectively, and both compounds contained tetrahedrally coordinated boron
16 Chapter 1
129
and consisted of polymeric anionic chains. The perselenoborates RbBSe3,
TlBSe3, and CsBSe3 have been prepared and all three compounds contained
polymeric anionic chains with spirocyclically fused five-membered B2Se3 rings
in which the B atoms were in a tetrahedral BSe4 coordination.144 The lithium
perselenoborate Li2B2Se5 had a novel three-dimensional anion network with B
atoms in tetrahedral BSe4 coordination.145 LiBSe3 has been synthesized and it
also possessed a novel polymeric network.146 The perthioborates Na2B2S5 and
Li2B2S5 had structures containing planar B2S52
groups consisting of five-
membered B2S3 rings with one additional exocyclic S atoms on each B.139 The
first alkaline earth perselenoborates BaB2Se6 and BaB4Se13 were synthesized
from appropriate amounts of barium selenide, boron, and selenium at
high temperatures.147 The synthesis of Na2B2Se7, K2B2S7, and K2B2Se7 has
been reported with their structures contained polymeric B2E72
anion chains
formed by spirocyclically connected five-membered B2E3 and six-membered
B2E4 rings.148 Heating, followed by annealing of stoichiometric quantities of
Li2S, B, and S8, afforded the thioborates Li5B9S13 (730 1C) and Li9B19S33
(700 1C) and their crystal structures displayed interpenetrating polymeric
boron–sulfur anionic networks.149 New isotypic crystalline phases of
Sr4.2Ba2.8(BS3)4S and Ba7(BSe3)4Se were obtained through systematic studies
on quarternary thioborates and selenoborates containing the heavier alkaline
earth metals.150
The thioborate Na6B10S18, composed of B10S20 units linked through tetra-
hedral corners, was shown to be a highly polymeric macrotetrahedral 3d
network.151 New polymeric-layered anion networks composed of corner-
sharing super-adamantane-type B10E20 units, connected by Li and Cs cations
were observed in Li6
xCsxB10E18 (xB1; E¼S, Se) and Na6B10Se18.152 Lithium
selenoborates such as Li6
2xBa11xB10Se19 and Li31xNa5
xB10Se19, which have
severely disordered cations, were reported as excellent candidates for mecha-
nistic analysis of ionic conductivity measurements.153,154 Similarly,
Li6
2xSr21xB10Se20 (x ¼ 0.7) has also been studied.155
The selenoborate Cs8[B12(BSe3)6] (Cs830) was obtained from the reaction of
caesium selenide, boron, and selenium by means of a high-temperature solid-
state synthesis (Figure 5).156 The retention of the icosahedral boron network
during this reaction has been noted as very unusual.157 The three selenaborates
Rb830, Rb4Hg230, and Cs4Hg230, prepared from the metal selenides, amor-
phous boron, and selenium in solid-state reactions at 700 1C, also contained the
B12 icosahedral unit saturated with six trigonal-planar BSe3 entities.158 Sys-
tematic studies of icosahedral-B12 containing selenoborates with alkali metal
cations have led to a new crystalline phase for Na6[B18Se17], which contained
neighbouring {B12Se18} cluster moieties connected in one direction via exocyclic
Se atoms in an infinite-chain anion.159 A new crystalline phase of K830 has been
obtained with the selenoborato anion showing three different substitution
patterns.160 New crystalline phases of Rb830 and Cs830 have been re-
ported by reaction of amorphous boron with alkali metal sulfide and sulfur
at B600 1C in evacuated carbon-coated silica tubes.161
Compounds Containing the Boron–Chalcogen Bond 17

Figure 5 Unit cell of Cs8[B12(BSe3)6], (Cs830)

(Reproduced with permission from Angew. Chem., Int. Ed. Engl., 1997,
36, 1903.)

1.5 Heterocycles Containing B–E Linkages

The first stable disulfanylborane (Tbt)B(SH)2 (31) was prepared by reaction of
the overcrowded lithium hydroborate, (Tbt)BH3Li(thf)3 with S8.162 Dilithiation
of 31 followed by treatment with electrophiles such as Cp2TiCl2, (mes)2GeBr2,
PhSnCl2, and (Tbt)SbBr2 resulted in the isolation of novel four-membered 1,3-
dithiaboretane rings (ERn ¼ TiCp2, Ge(mes)2, SnPh2 (32,
Figure 6), or Sb{Tbt}); the structures of these ring systems were confirmed in all
cases by single-crystal XRD studies.162,163
B2H6 was shown to react with H2S2, H2S3, or crude sulfane oil to form the
1,2,4,3,5-trithiadiborolane, H2B2S3.164 The reaction of tBu2S2 with ArBBr2
(Ar¼Ph, 2-MeC6H4, 3-MeC6H4, 4-MeC6H4, 4-EtC6H4, 3,5-Me2C6H3) in ref-
luxing toluene gave the thermally stable, moisture-sensitive 1,2,4,3,5-
trithiadiborolanes, Ar2B2S3.165 The reaction of ArBBr2 with HgS in benzene
at reflux produced a series of 1,3,5-triarylborthiins (Ar3B3S3), which were found
to be less stable than Ph3B3S3 and were significantly decomposed to mixed B/O/
S rings (e.g. Ar3B3S2O, Ar3B3SO2) within minutes in air.166 Reaction of the
ArBBr2 species with (Me3Si)2S in benzene at room temperature afforded the
corresponding 1,3,5-triarylborthiins, and not the expected 1,3,2,4-di-
thiadiboretanes (Ar2B2S2), while the reaction of S8 with PhBBr2 or
18 Chapter 1

Figure 6 ORTEP drawing of (Tbt)BS2SnPh2 (32)

(Reproduced with permission from Organometallics, 1997, 16, 4316.)

4-MeC6H4BBr2 was investigated by 11B NMR and mass spectrometry and

cyclic RBSn species were identified.166 A theoretical study of the structures and
energetics and magnetic properties of H3B3E3 (E¼O, S, Se) has been reported
with the discussion centred on the relative aromaticity of these rings compared
to those of related group 15 boron heterocycles.167
The triselenadiborolanes 3,5-R2-1,2,4,3,5-Se3B2 {R¼Et (33), Pr} readily
formed coordination adducts with two equivalents of pyridine, 3,5-dime-
thylpyridine, and 3-chloropyridine.168 With one equivalent of base, only one
of the B atoms became coordinated, and surprisingly, the system was not
fluxional at room temperature.168 The addition of two equivalents of pyrazole
to 33 (Scheme 7) resulted in a brown suspension and a yellow solution. Crystals
of a B2N4Se2-bicyclo[2.2.2]octane were formed upon cooling this solution to

80 1C. With bulkier pyrazole derivatives (e.g. 3-methylpyrazole, 3-phenyl-
pyrazole), the B2N4Se-bicyclo[2.2.1] heptanes were formed.169
Compounds Containing the Boron–Chalcogen Bond 19

HS SH

(Me3Si)2HC CH(SiMe3)2

Se Se

EtB BEt
CH(SiMe3)2 Se

31 33
Scheme 7

Elimination of hydrogen halides from dihalogenoorganylboranes by reaction

with ferrocene-1,1 0 -dithiol resulted in 1,3-dithia-2-boryl[3]ferrocenophanes.170
These borylferrocenophanes were air sensitive, but were characterized by
NMR, MS, and elemental analysis.170 A series of 1,3-dibora-2-X-[3]fer-
rocenophanes (X¼S, Se, Te) were prepared and characterized and the crystal
structure of [Se{NiPr2)BC5H4}2Fe] has been reported.171
The first organoborontellurium compound was prepared from the reaction
of 9-Cl-9-BBN with Na2Te2 and Na2Te. The product, (9-BBN)2Te, reacted
with water to give elemental Te, (9-BBN)2O and (9-H-9-BBN)2.172
The 1,2-benzothiaborolidine, a heteroaromatic analogue of indenyl, has been
prepared and shown to form a Z5-complex with RuCp*.173 The related anion,
2-(diisopropylamino)-1,2-thiaborolide(1-) has also been prepared and coordi-
nated to Ru in [{(iPr2N)BSC3H3}RuCp*] (34, Figure 7) and Zr in
[{(iPr2N)BSC3H3}ZrCl2Cp*].174

1.6 Miscellaneous Boron–Chalcogen Compounds and

Reagents
The use of bulky aryl substituents allowed the structural characterization of the
monomeric B–S compounds, mes2BSPh and (2,4,6-Pri3C6H2) B(SPh)2, showing
short B–S distances (180 pm) consistent with B–S p-interaction. Barriers to
rotation of 18.4 and 12 kcal mol
1 were determined by variable temperature
NMR studies.175 A thioxoborane (Tbt)BS, with a B¼S bond and the very bulky
aryl group on the B atom was obtained from the thermolysis of an overcrowded
four-membered boracycle, 1,3,2,-dithiastannaboretane.176 The barrier to rota-
tion about B¼E bonds of coordinatively unsaturated borates and thiaborates
has also been discussed with the lower rotational barrier in the O derivatives
attributed to greater stabilization of the transition state.177 The rotational
barriers did not reflect the relative strengths of the B¼E p bonds.177
20 Chapter 1

Figure 7 Solid-state structure of [{(iPr2N)BSC3H3}RuCp*] (34)

(Reproduced with permission from Organometallics, 2000, 19, 4937.)

n-Octadecanethiol was found to react with B(C6F5)3 to yield an equilibrium

mixture of reactants and the 1:1 adduct, and the adduct was deprotonated by
‘proton-sponge’ to yield the salt [C10H6(NMe2)2H][(n-C18H37S)B(C6F5)3].178
Reaction with Cp*MMe3 (M¼Ti, Hf) yielded [Cp*MMe2][(n-C18H37S)
B(C6F5)3], which was a good initiator for the copolymerization of isobutene
with isoprene in high conversions to high molecular weight copolymers.179 The
crystal structure of the tetrathiophene adduct of tris(pentafluorophenyl)borane,
(C4H8S)B(C6F5)3, was reported and it showed a comparatively long BS dis-
tance of 2.0843 Å.180 Metal-catalyzed additions of B–X (X¼H, B) bonds to
thiocarbonyl compounds and vinyl sulfides afforded a-thioboronate esters.181
The reaction of BH3.thf with NaSH or anhydrous Na2S, or the reaction of
BH3.thf/Na[BH4] (2:1) with excess H2S, produced the adamantine-like com-
pound Na2[(BH2)6S4].182 The analogous selenium compound was obtained
from the reaction of elemental Se with Na[BH4] (1:1) in diglyme. The X-ray
structures of both of these cage anions were determined.182 The reaction of
Na[BH4]/BH3.thf with S8 proceeded with elimination of H2 and gave
Na[(BH2)5S4] with a noradamanatane-like {B5S4} skeleton.183 The salt [Na
(triglyme)]2[S(BH3)4], which contained an anion isoelectronic with [SO4]2
, was
obtained from the reaction of Na[BH4] with Na[H3B-m2-S(B2H5)] in
triglyme.184
Compounds Containing the Boron–Chalcogen Bond 21




Potentially chelating [H2B(SPh)2] , [HB(SPh)3] , and [B(SPh)4] ligands
have been prepared and their reactions with 3d transition-metal complexes
were investigated.185 The synthesis, characterization, and reactivity of the S-
rich tridentate ligand tetrakis(2-thienyl)borate anion was reported; unlike
[(MeS)4B]
, it did not coordinate to {Mo(CO)3} when reacted with
[(C7H8)Mo(CO)3].186 Stabilization of the tetrathioborato ligand has been
achieved in novel sulfido niobium clusters. Thus, the neutral diamagnetic
complex, [Nb3Cp3S3(S3BSH)] (35, Figure 8), was obtained in yields of up to
28% by reaction of S8 with [Nb2Cp2(B2H6)2] in decane at 170 1C.187
Finally, this section reports on a few unusual reactions of B–E-containing
compounds in which they serve as reagents, with loss of chalcogen. A novel
route for the synthesis of icosahedral closo-RNB11H11 (R ¼ tBuCH2, Ph)
clusters involving the use of BH3.SMe2 and nido-RNB9H11 in decalin at 170 1C
has been reported.184 The reaction of ClBH2.SMe2 and proton sponge and
NaH with nido-B10H14 leads to the formation of [B11H14]
.188 The synthesis
and characterization of the first example of a three-membered borocyclopro-
pane ring coordinated to a trimetal fragment, [Fe3(CO)9(Z3-BHCHCMe}], has
been reported; it was obtained in low yield from the reaction of BH2Br.SMe2
with [Fepy6][Fe4(CO)13].189 The two metallaboranes [Co2(CO)6B2H4] and
[Co5(CO)13(m-CO)B2H] were prepared in low yield by reaction of [Co2(CO)8]
with BH3.SMe2; both compounds were characterized by XRD and the former
compound was isoelectronic with [Fe2(CO)6B2H6] and [Co2(CO)6C2H2].190

Figure 8 Structure of [Nb3Cp3S3(S3BSH)] (35)

(Reproduced with permission from Angew. Chem., Int. Ed. Engl., 1992,
31, 1022.)
22 Chapter 1
. .
BH3 SMe2 readily reacted with P4O6 and formed the adduct P4O6 BH3, which
was shown to dimerize spontaneously at
30 1C to P8O12(BH3)2.191

Abbreviations

Arene any derivative of C6H6

Aryl any derivative of C6H5
9-BBN 9-borabicyclo[3.3.1]nonane
Cp C5H5

Cp* C5Me5

Tbt 2,4,6-[Me3Si2HC]3C6H2
Thf tetrahydrofuran

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82. M. Murphy, T.R. Spalding, J.D. Kennedy, M. Thornton-Pett, K.M.A.
Malik, M.B. Hursthouse and J. Holub, J. Chem. Soc., Chem. Commun.,
1994, 2403.
83. G. Ferguson, D.E. McCarthy, T.R. Spalding and J.D. Kennedy, Acta
Crystallogr., Sect. C, 1996, 52, 548.
84. J.H. Jones, X.L.R. Fontaine, N.N. Greenwood, J.D. Kennedy, M.
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26 Chapter 1
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94. G.M. Rosair, A.J. Welch and A.S. Weller, Acta Crystallogr., Sect. C,
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Kennedy and M. Thornton-Pett, J. Chem. Soc., Dalton Trans, 1990, 1819.
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Another Random Scribd Document
with Unrelated Content
 “What I can’t make out,” said Teddy Weeks, “is how on earth the
brute came to be in my room. Somebody must have put him there.
The whole thing is very mysterious.”

“Why didn’t he pin you?” demanded Ukridge again.

“Oh, I managed to climb on to the top of the wardrobe while he

was biting Beamish,” said Teddy Weeks. “And then the landlady
came and took him away. But I can’t stop here talking. I must go
and get that doctor.”

We gazed after him in silence as he tripped down the street. We

noted the careful manner in which he paused at the corner to eye
the traffic before crossing the road, the wary way in which he drew
back to allow a truck to rattle past.

“You heard that?” said Ukridge, tensely. “He climbed on to the top
of the wardrobe!”

“Yes.”

“And you saw the way he dodged that excellent truck?”

“Yes.”

“Something’s got to be done,” said Ukridge, firmly. “The man has

got to be awakened to a sense of his responsibilities.”

Next day a deputation waited on Teddy Weeks.

Ukridge was our spokesman, and he came to the point with

admirable directness.

“How about it?” asked Ukridge.

“How about what?” replied Teddy Weeks, nervously, avoiding his

accusing eye.
 “When do we get action?”

“Oh, you mean that accident business?”

“Yes.”

“I’ve been thinking about that,” said Teddy Weeks.

Ukridge drew the mackintosh which he wore indoors and out of

doors and in all weathers more closely around him. There was in the
action something suggestive of a member of the Roman Senate
about to denounce an enemy of the State. In just such a manner
must Cicero have swished his toga as he took a deep breath
preparatory to assailing Clodius. He toyed for a moment with the
ginger-beer wire which held his pince-nez in place, and endeavoured
without success to button his collar at the back. In moments of
emotion Ukridge’s collar always took on a sort of temperamental
jumpiness which no stud could restrain.

“And about time you were thinking about it,” he boomed, sternly.

We shifted appreciatively in our seats, all except Victor Beamish,

who had declined a chair and was standing by the mantelpiece.
“Upon my Sam, it’s about time you were thinking about it. Do you
realise that we’ve invested an enormous sum of money in you on the
distinct understanding that we could rely on you to do your duty and
get immediate results? Are we to be forced to the conclusion that
you are so yellow and few in the pod as to want to evade your
honourable obligations? We thought better of you, Weeks. Upon my
Sam, we thought better of you. We took you for a two-fisted,
enterprising, big-souled, one hundred-per-cent. he-man who would
stand by his friends to the finish.”

“Yes, but——”

“Any bloke with a sense of loyalty and an appreciation of what it

meant to the rest of us would have rushed out and found some
means of fulfilling his duty long ago. You don’t even grasp at the
opportunities that come your way. Only yesterday I saw you draw
back when a single step into the road would have had a truck
bumping into you.”

“Well, it’s not so easy to let a truck bump into you.”

“Nonsense. It only requires a little ordinary resolution. Use your

imagination, man. Try to think that a child has fallen down in the
street—a little golden-haired child,” said Ukridge, deeply affected.
“And a dashed great cab or something comes rolling up. The kid’s
mother is standing on the pavement, helpless, her hands clasped in
agony. ‘Dammit,’ she cries, ‘will no one save my darling?’ ‘Yes, by
George,’ you shout, ‘I will.’ And out you jump and the thing’s over in
half a second. I don’t know what you’re making such a fuss about.”

“Yes, but——” said Teddy Weeks.

“I’m told, what’s more, it isn’t a bit painful. A sort of dull shock,
that’s all.”

“Who told you that?”

“I forget. Someone.”

“Well, you can tell him from me that he’s an ass,” said Teddy
Weeks, with asperity.

“All right. If you object to being run over by a truck there are lots
of other ways. But, upon my Sam, it’s pretty hopeless suggesting
them. You seem to have no enterprise at all. Yesterday, after I went
to all the trouble to put a dog in your room, a dog which would have
done all the work for you—all that you had to do was stand still and
let him use his own judgment—what happened? You climbed on to
——”
 Victor Beamish interrupted, speaking in a voice husky with
emotion.

“Was it you who put that damned dog in the room?”

“Eh?” said Ukridge. “Why, yes. But we can have a good talk about
all that later on,” he proceeded, hastily. “The point at the moment is
how the dickens we’re going to persuade this poor worm to collect
our insurance money for us. Why, damme, I should have thought
you would have——”

“All I can say——” began Victor Beamish, heatedly.

“Yes, yes,” said Ukridge; “some other time. Must stick to business
now, laddie. I was saying,” he resumed, “that I should have thought
you would have been as keen as mustard to put the job through for
your own sake. You’re always beefing that you haven’t any clothes
to impress managers with. Think of all you can buy with your share
of the swag once you have summoned up a little ordinary
determination and seen the thing through. Think of the suits, the
boots, the hats, the spats. You’re always talking about your dashed
career, and how all you need to land you in a West-end production is
good clothes. Well, here’s your chance to get them.”

His eloquence was not wasted. A wistful look came into Teddy
Weeks’s eye, such a look as must have come into the eye of Moses
on the summit of Pisgah. He breathed heavily. You could see that
the man was mentally walking along Cork Street, weighing the
merits of one famous tailor against another.

“I’ll tell you what I’ll do,” he said, suddenly. “It’s no use asking me
to put this thing through in cold blood. I simply can’t do it. I haven’t
the nerve. But if you fellows will give me a dinner to-night with lots
of champagne I think it will key me up to it.”

A heavy silence fell upon the room. Champagne! The word was
like a knell.
 “How on earth are we going to afford champagne?” said Victor
Beamish.

“Well, there it is,” said Teddy Weeks. “Take it or leave it.”

“Gentlemen,” said Ukridge, “it would seem that the company

requires more capital. How about it, old horses? Let’s get together in
a frank, business-like cards-on-the-table spirit, and see what can be
done. I can raise ten bob.”

“What!” cried the entire assembled company, amazed. “How?”

“I’ll pawn a banjo.”

“You haven’t got a banjo.”

“No, but George Tupper has, and I know where he keeps it.”

Started in this spirited way, the subscriptions came pouring in. I

contributed a cigarette-case, Bertram Fox thought his landlady would
let him owe for another week, Robert Dunhill had an uncle in
Kensington who, he fancied, if tactfully approached, would be good
for a quid, and Victor Beamish said that if the advertisement-
manager of the O-So-Eesi Piano-Player was churlish enough to
refuse an advance of five shillings against future work he misjudged
him sadly. Within a few minutes, in short, the Lightning Drive had
produced the impressive total of two pounds six shillings, and we
asked Teddy Weeks if he thought that he could get adequately keyed
up within the limits of that sum.

“I’ll try,” said Teddy Weeks.

So, not unmindful of the fact that that excellent hostelry supplied
champagne at eight shillings the quart bottle, we fixed the meeting
for seven o’clock at Barolini’s.
 Considered as a social affair, Teddy Weeks’s keying-up dinner was
not a success. Almost from the start I think we all found it trying. It
was not so much the fact that he was drinking deeply of Barolini’s
eight-shilling champagne while we, from lack of funds, were
compelled to confine ourselves to meaner beverages; what really
marred the pleasantness of the function was the extraordinary effect
the stuff had on Teddy. What was actually in the champagne
supplied to Barolini and purveyed by him to the public, such as were
reckless enough to drink it, at eight shillings the bottle remains a
secret between its maker and his Maker; but three glasses of it were
enough to convert Teddy Weeks from a mild and rather oily young
man into a truculent swashbuckler.

He quarrelled with us all. With the soup he was tilting at Victor

Beamish’s theories of Art; the fish found him ridiculing Bertram Fox’s
views on the future of the motion-picture; and by the time the leg of
chicken with dandelion salad arrived—or, as some held, string salad
—opinions varied on this point—the hell-brew had so wrought on
him that he had begun to lecture Ukridge on his mis-spent life and
was urging him in accents audible across the street to go out and
get a job and thus acquire sufficient self-respect to enable him to
look himself in the face in a mirror without wincing. Not, added
Teddy Weeks with what we all thought uncalled-for offensiveness,
that any amount of self-respect was likely to do that. Having said
which, he called imperiously for another eight bobs’-worth.

We gazed at one another wanly. However excellent the end

towards which all this was tending, there was no denying that it was
hard to bear. But policy kept us silent. We recognised that this was
Teddy Weeks’s evening and that he must be humoured. Victor
Beamish said meekly that Teddy had cleared up a lot of points which
had been troubling him for a long time. Bertram Fox agreed that
there was much in what Teddy had said about the future of the
close-up. And even Ukridge, though his haughty soul was seared to
its foundations by the latter’s personal remarks, promised to take his
homily to heart and act upon it at the earliest possible moment.
 “You’d better!” said Teddy Weeks, belligerently, biting off the end
of one of Barolini’s best cigars. “And there’s another thing—don’t let
me hear of your coming and sneaking people’s socks again.”

“Very well, laddie,” said Ukridge, humbly.

“If there is one person in the world that I despise,” said Teddy,
bending a red-eyed gaze on the offender, “it’s a snock-seeker—a
seek-snocker—a—well, you know what I mean.”

We hastened to assure him that we knew what he meant and he

relapsed into a lengthy stupor, from which he emerged three-
quarters of an hour later to announce that he didn’t know what we
intended to do, but that he was going. We said that we were going
too, and we paid the bill and did so.

Teddy Weeks’s indignation on discovering us gathered about him

upon the pavement outside the restaurant was intense, and he
expressed it freely. Among other things, he said—which was not true
—that he had a reputation to keep up in Soho.

“It’s all right, Teddy, old horse,” said Ukridge, soothingly. “We just
thought you would like to have all your old pals round you when you
did it.”

“Did it? Did what?”

“Why, had the accident.”

Teddy Weeks glared at him truculently. Then his mood seemed to

change abruptly, and he burst into a loud and hearty laugh.

“Well, of all the silly ideas!” he cried, amusedly. “I’m not going to
have an accident. You don’t suppose I ever seriously intended to
have an accident, do you? It was just my fun.” Then, with another
sudden change of mood, he seemed to become a victim to an acute
unhappiness. He stroked Ukridge’s arm affectionately, and a tear
rolled down his cheek. “Just my fun,” he repeated. “You don’t mind
my fun, do you?” he asked, pleadingly. “You like my fun, don’t you?
All my fun. Never meant to have an accident at all. Just wanted
dinner.” The gay humour of it all overcame his sorrow once more.
“Funniest thing ever heard,” he said cordially. “Didn’t want accident,
wanted dinner. Dinner daxident, danner dixident,” he added, driving
home his point. “Well, good night all,” he said, cheerily. And,
stepping off the kerb on to a banana-skin, was instantly knocked ten
feet by a passing lorry.

“Two ribs and an arm,” said the doctor five minutes later,
superintending the removal proceedings. “Gently with that stretcher.”

It was two weeks before we were informed by the authorities of

Charing Cross Hospital that the patient was in a condition to receive
visitors. A whip-round secured the price of a basket of fruit, and
Ukridge and I were deputed by the shareholders to deliver it with
their compliments and kind enquiries.

“Hallo!” we said in a hushed, bedside manner when finally

admitted to his presence.

“Sit down, gentlemen,” replied the invalid.

I must confess even in that first moment to having experienced a

slight feeling of surprise. It was not like Teddy Weeks to call us
gentlemen. Ukridge, however, seemed to notice nothing amiss.

“Well, well, well,” he said, buoyantly. “And how are you, laddie?
We’ve brought you a few fragments of fruit.”

“I am getting along capitally,” replied Teddy Weeks, still in that

odd precise way which had made his opening words strike me as
curious. “And I should like to say that in my opinion England has
reason to be proud of the alertness and enterprise of her great
journals. The excellence of their reading-matter, the ingenuity of
their various competitions, and, above all, the go-ahead spirit which
has resulted in this accident insurance scheme are beyond praise.
Have you got that down?” he enquired.

Ukridge and I looked at each other. We had been told that Teddy
was practically normal again, but this sounded like delirium.

“Have we got that down, old horse?” asked Ukridge, gently.

Teddy Weeks seemed surprised.

“Aren’t you reporters?”

“How do you mean, reporters?”

“I thought you had come from one of these weekly papers that
have been paying me insurance money, to interview me,” said Teddy
Weeks.

Ukridge and I exchanged another glance. An uneasy glance this

time. I think that already a grim foreboding had begun to cast its
shadow over us.

“Surely you remember me, Teddy, old horse?” said Ukridge,

anxiously.

Teddy Weeks knit his brow, concentrating painfully.

“Why, of course,” he said at last. “You’re Ukridge, aren’t you?”

“That’s right. Ukridge.”

“Of course. Ukridge.”

“Yes. Ukridge. Funny your forgetting me!”

“Yes,” said Teddy Weeks. “It’s the effect of the shock I got when
that thing bowled me over. I must have been struck on the head, I
suppose. It has had the effect of rendering my memory rather
uncertain. The doctors here are very interested. They say it is a
most unusual case. I can remember some things perfectly, but in
some ways my memory is a complete blank.”

“Oh, but I say, old horse,” quavered Ukridge. “I suppose you

haven’t forgotten about that insurance, have you?”

“Oh, no, I remember that.”

Ukridge breathed a relieved sigh.

“I was a subscriber to a number of weekly papers,” went on Teddy

Weeks. “They are paying me insurance money now.”

“Yes, yes, old horse,” cried Ukridge. “But what I mean is you
remember the Syndicate, don’t you?”

Teddy Weeks raised his eyebrows.

“Syndicate? What Syndicate?”

“Why, when we all got together and put up the money to pay for
the subscriptions to these papers and drew lots, to choose which of
us should go out and have an accident and collect the money. And
you drew it, don’t you remember?”

Utter astonishment, and a shocked astonishment at that, spread

itself over Teddy Weeks’s countenance. The man seemed outraged.

“I certainly remember nothing of the kind,” he said, severely. “I

cannot imagine myself for a moment consenting to become a party
to what from your own account would appear to have been a
criminal conspiracy to obtain money under false pretences from a
number of weekly papers.”

“But, laddie——”
 “However,” said Teddy Weeks, “if there is any truth in this story, no
doubt you have documentary evidence to support it.”

Ukridge looked at me. I looked at Ukridge. There was a long

silence.

“Shift-ho, old horse?” said Ukridge, sadly. “No use staying on

here.”

“No,” I replied, with equal gloom. “May as well go.”

“Glad to have seen you,” said Teddy Weeks, “and thanks for the
fruit.”

The next time I saw the man he was coming out of a manager’s
office in the Haymarket. He had on a new Homburg hat of a delicate
pearl grey, spats to match, and a new blue flannel suit, beautifully
cut, with an invisible red twill. He was looking jubilant, and; as I
passed him, he drew from his pocket a gold cigarette-case.

It was shortly after that, if you remember, that he made a big hit
as the juvenile lead in that piece at the Apollo and started on his
sensational career as a matinee idol.

Inside the church the organ had swelled into the familiar music of
the Wedding March. A verger came out and opened the doors. The
five cooks ceased their reminiscences of other and smarter weddings
at which they had participated. The camera-men unshipped their
cameras. The costermonger moved his barrow of vegetables a pace
forward. A dishevelled and unshaven man at my side uttered a
disapproving growl.

“Idle rich!” said the dishevelled man.

Out of the church came a beauteous being, leading attached to his

arm another being, somewhat less beauteous.
 There was no denying the spectacular effect of Teddy Weeks. He
was handsomer than ever. His sleek hair, gorgeously waved, shone
in the sun, his eyes were large and bright; his lissome frame, garbed
in faultless morning-coat and trousers, was that of an Apollo. But his
bride gave the impression that Teddy had married money. They
paused in the doorway, and the camera-men became active and
fussy.

“Have you got a shilling, laddie?” said Ukridge in a low, level voice.

“Why do you want a shilling?”

“Old horse,” said Ukridge, tensely, “it is of the utmost vital

importance that I have a shilling here and now.”

I passed it over. Ukridge turned to the dishevelled man, and I

perceived that he held in his hand a large rich tomato of juicy and
over-ripe appearance.

“Would you like to earn a bob?” Ukridge said.

“Would I!” replied the dishevelled man.

Ukridge sank his voice to a hoarse whisper.

The camera-men had finished their preparations. Teddy Weeks,

his head thrown back in that gallant way which has endeared him to
so many female hearts, was exhibiting his celebrated teeth. The
cooks, in undertones, were making adverse comments on the
appearance of the bride.

“Now, please,” said one of the camera-men.

Over the heads of the crowd, well and truly aimed, whizzed a
large juicy tomato. It burst like a shell full between Teddy Weeks’s
expressive eyes, obliterating them in scarlet ruin. It spattered Teddy
Weeks’s collar, it dripped on Teddy Weeks’s morning-coat. And the
dishevelled man turned abruptly and raced off down the street.

Ukridge grasped my arm. There was a look of deep content in his

eyes.

“Shift-ho?” said Ukridge.

Arm-in-arm, we strolled off in the pleasant June sunshine.

 CHAPTER III
THE DÉBUT OF BATTLING BILLSON

It becomes increasingly difficult, I have found, as time goes by, to

recall the exact circumstances in which one first became acquainted
with this man or that; for as a general thing I lay no claim to the
possession of one of those hair-trigger memories which come from
subscribing to the correspondence courses advertised in the
magazines. And yet I can state without doubt or hesitation that the
individual afterwards known as Battling Billson entered my life at
half-past four on the afternoon of Saturday, September the tenth,
two days after my twenty-seventh birthday. For there was that about
my first sight of him which has caused the event to remain
photographically lined on the tablets of my mind when a yesterday
has faded from its page. Not only was our meeting dramatic and
even startling, but it had in it something of the quality of the last
straw, the final sling or arrow of outrageous Fortune. It seemed to
put the lid on the sadness of life.

Everything had been going steadily wrong with me for more than
a week. I had been away, paying a duty visit to uncongenial relatives
in the country, and it had rained and rained and rained. There had
been family prayers before breakfast and bezique after dinner. On
the journey back to London my carriage had been full of babies, the
train had stopped everywhere, and I had had nothing to eat but a
bag of buns. And when finally I let myself into my lodgings in Ebury
Street and sought the soothing haven of my sitting-room, the first
thing I saw on opening the door was this enormous red-headed man
lying on the sofa.

He made no move as I came in, for he was asleep; and I can best
convey the instantaneous impression I got of his formidable
physique by saying that I had no desire to wake him. The sofa was a
small one, and he overflowed it in every direction. He had a broken
nose, and his jaw was the jaw of a Wild West motion-picture star
registering Determination. One hand was under his head; the other,
hanging down to the floor, looked like a strayed ham congealed into
stone. What he was doing in my sitting-room I did not know; but,
passionately as I wished to know, I preferred not to seek first-hand
information. There was something about him that seemed to
suggest that he might be one of those men who are rather cross
when they first wake up. I crept out and stole softly downstairs to
make enquiries of Bowles, my landlord.

“Sir?” said Bowles, in his fruity ex-butler way, popping up from the
depths accompanied by a rich smell of finnan haddie.

“There’s someone in my room,” I whispered.

“That would be Mr. Ukridge, sir.”

“It wouldn’t be anything of the kind,” I replied, with asperity. I

seldom had the courage to contradict Bowles, but this statement
was so wildly inaccurate that I could not let it pass. “It’s a huge red-
headed man.”

“Mr. Ukridge’s friend, sir. He joined Mr. Ukridge here yesterday.”

“How do you mean, joined Mr. Ukridge here yesterday?”

“Mr. Ukridge came to occupy your rooms in your absence, sir, on

the night after your departure. I assumed that he had your approval.
He said, if I remember correctly, that ‘it would be all right.’”

For some reason or other which I had never been able to explain,
Bowles’s attitude towards Ukridge from their first meeting had been
that of an indulgent father towards a favourite son. He gave the
impression now of congratulating me on having such a friend to rally
round and sneak into my rooms when I went away.

“Would there be anything further, sir?” enquired Bowles, with a

wistful half-glance over his shoulder. He seemed reluctant to tear
himself away for long from the finnan haddie.

“No,” I said. “Er—no. When do you expect Mr. Ukridge back?”

“Mr. Ukridge informed me that he would return for dinner, sir.

Unless he has altered his plans, he is now at a matinée performance
at the Gaiety Theatre.”

The audience was just beginning to leave when I reached the

Gaiety. I waited in the Strand, and presently was rewarded by the
sight of a yellow mackintosh working its way through the crowd.

“Hallo, laddie!” said Stanley Featherstonehaugh Ukridge, genially.

“When did you get back? I say, I want you to remember this tune,
so that you can remind me of it to-morrow, when I’ll be sure to have
forgotten it. This is how it goes.” He poised himself flat-footedly in
the surging tide of pedestrians and, shutting his eyes and raising his
chin, began to yodel in a loud and dismal tenor. “Tumty-tumty-
tumty-tum, tum tum tum,” he concluded. “And now, old horse, you
may lead me across the street to the Coal Hole for a short snifter.
What sort of a time have you had?”

“Never mind what sort of a time I’ve had. Who’s the fellow you’ve
dumped down in my rooms?

“Red-haired man?”
 “Good Lord! Surely even you wouldn’t inflict more than one on
me?”

Ukridge looked at me a little pained.

“I don’t like this tone,” he said, leading me down the steps of the
Coal Hole. “Upon my Sam, your manner wounds me, old horse. I
little thought that you would object to your best friend laying his
head on your pillow.”

“I don’t mind your head. At least I do, but I suppose I’ve got to
put up with it. But when it comes to your taking in lodgers——”

“Order two tawny ports, laddie,” said Ukridge, “and I’ll explain all
about that. I had an idea all along that you would want to know. It’s
like this,” he proceeded, when the tawny ports had arrived. “That
bloke’s going to make my everlasting fortune.”

“Well, can’t he do it somewhere else except in my sitting-room?”

“You know me, old horse,” said Ukridge, sipping luxuriously.

“Keen, alert, far-sighted. Brain never still. Always getting ideas—bing
—like a flash. The other day I was in a pub down Chelsea way
having a bit of bread and cheese, and a fellow came in smothered
with jewels. Smothered, I give you my word. Rings on his fingers
and a tie-pin you could have lit your cigar at. I made enquiries and
found that he was Tod Bingham’s manager.”

“Who’s Tod Bingham?”

“My dear old son, you must have heard of Tod Bingham. The new
middle-weight champion. Beat Alf Palmer for the belt a couple of
weeks ago. And this bloke, as opulent-looking a bloke as ever I saw,
was his manager. I suppose he gets about fifty per cent. of
everything Tod makes, and you know the sort of purses they give for
big fights nowadays. And then there’s music-hall tours and the
movies and all that. Well, I see no reason why, putting the thing at
the lowest figures, I shouldn’t scoop in thousands. I got the idea two
seconds after they told me who this fellow was. And what made the
thing seem almost as if it was meant to be was the coincidence that
I should have heard only that morning that the Hyacinth was in.”

The man seemed to me to be rambling. In my reduced and

afflicted state his cryptic method of narrative irritated me.

“I don’t know what you’re talking about,” I said. “What’s the

Hyacinth? In where?”

“Pull yourself together, old horse,” said Ukridge, with the air of one
endeavouring to be patient with a half-witted child. “You remember
the Hyacinth, the tramp steamer I took that trip on a couple of years
ago. Many’s the time I’ve told you all about the Hyacinth. She
docked in the Port of London the night before I met this opulent
bloke, and I had been meaning to go down next day and have a
chat with the lads. The fellow you found in your rooms is one of the
trimmers. As decent a bird as ever you met. Not much conversation,
but a heart of gold. And it came across me like a thunderbolt the
moment they told me who the jewelled cove was that, if I could only
induce this man Billson to take up scrapping seriously, with me as his
manager, my fortune was made. Billson is the man who invented
fighting.”

“He looks it.”

“Splendid chap—you’ll like him.”

“I bet I shall. I made up my mind to like him the moment I saw

him.”

“Never picks a quarrel, you understand—in fact, used to need the

deuce of a lot of provocation before he would give of his best; but
once he started—golly! I’ve seen that man clean out a bar at
Marseilles in a way that fascinated you. A bar filled to overflowing
with A.B.’s and firemen, mind you, and all capable of felling oxen
with a blow. Six of them there were, and they kept swatting Billson
with all the vim and heartiness at their disposal, but he just let them
bounce off, and went on with the business in hand. The man’s a
champion, laddie, nothing less. You couldn’t hurt him with a hatchet,
and every time he hits anyone all the undertakers in the place jump
up and make bids for the body. And the amazing bit of luck is that
he was looking for a job ashore. It appears he’s fallen in love with
one of the barmaids at the Crown in Kennington. Not,” said Ukridge,
so that all misapprehension should be avoided, “the one with the
squint. The other one. Flossie. The girl with yellow hair.”

“I don’t know the barmaids at the Crown in Kennington,” I said.

“Nice girls,” said Ukridge, paternally. “So it was all right, you see.
Our interests were identical. Good old Billson isn’t what you’d call a
very intelligent chap, but I managed to make him understand after
an hour or so, and we drew up the contract. I’m to get fifty per cent.
of everything in consideration of managing him, fixing up fights, and
looking after him generally.”

“And looking after him includes tucking him up on my sofa and

singing him to sleep?”

Again that pained look came into Ukridge’s face. He gazed at me

as if I had disappointed him.

“You keep harping on that, laddie, and it isn’t the right spirit.
Anyone would think that we had polluted your damned room.”

“Well, you must admit that having this coming champion of yours
in the home is going to make things a bit crowded.”

“Don’t worry about that, my dear old man,” said Ukridge,

reassuringly. “We move to the White Hart at Barnes to-morrow, to
start training. I’ve got Billson an engagement in one of the
preliminaries down at Wonderland two weeks from to-night.”
 “No; really?” I said, impressed by this enterprise. “How did you
manage it?”

“I just took him along and showed him to the management. They
jumped at him. You see, the old boy’s appearance rather speaks for
itself. Thank goodness, all this happened just when I had a few quid
tucked away. By the greatest good luck I ran into George Tupper at
the very moment when he had had word that they were going to
make him an under-secretary or something—I can’t remember the
details, but it’s something they give these Foreign Office blokes
when they show a bit of class—and Tuppy parted with a tenner
without a murmur. Seemed sort of dazed. I believe now I could have
had twenty if I’d had the presence of mind to ask for it. Still,” said
Ukridge, with a manly resignation which did him credit, “it can’t be
helped now, and ten will see me through. The only thing that’s
worrying me at the moment is what to call Billson.”

“Yes, I should be careful what I called a man like that.”

“I mean, what name is he to fight under?”

“Why not his own?”

“His parents, confound them,” said Ukridge, moodily, “christened

him Wilberforce. I ask you, can you see the crowd at Wonderland
having Wilberforce Billson introduced to them?”

“Willie Billson,” I suggested. “Rather snappy.”

Ukridge considered the proposal seriously, with knit brows, as

becomes a manager.

“Too frivolous,” he decided at length. “Might be all right for a

bantam, but—no, I don’t like it. I was thinking of something like
Hurricane Hicks or Rock-Crusher Riggs.”
 “Don’t do it,” I urged, “or you’ll kill his career right from the start.
You never find a real champion with one of these fancy names. Bob
Fitzsimmons, Jack Johnson, James J. Corbett, James J. Jeffries——”

“James J. Billson?”

“Rotten.”

“You don’t think,” said Ukridge, almost with timidity, “that Wildcat
Wix might do?”

“No fighter with an adjective in front of his name ever boxed in

anything except a three-round preliminary.”

“How about Battling Billson?”

I patted him on the shoulder.

“Go no farther,” I said. “The thing is settled. Battling Billson is the

name.”

“Laddie,” said Ukridge in a hushed voice, reaching across the table

and grasping my hand, “this is genius. Sheer genius. Order another
couple of tawny ports, old man.”

I did so, and we drank deep to the Battler’s success.

My formal introduction to my godchild took place on our return to

Ebury Street, and—great as had been my respect for the man before
—it left me with a heightened appreciation of the potentialities for
triumph awaiting him in his selected profession. He was awake by
this time and moving ponderously about the sitting-room, and he
looked even more impressive standing than he had appeared when
lying down. At our first meeting, moreover, his eyes had been closed
in sleep; they were now open, green in colour, and of a peculiarly
metallic glint which caused them, as we shook hands, to seem to be
exploring my person for good spots to hit. What was probably
intended to be the smile that wins appeared to me a grim and
sardonic twist of the lip. Take him for all in all, I had never met a
man so calculated to convert the most truculent swashbuckler to
pacifism at a glance; and when I recalled Ukridge’s story of the little
unpleasantness at Marseilles and realised that a mere handful of half
a dozen able-bodied seamen had had the temerity to engage this
fellow in personal conflict, it gave me a thrill of patriotic pride. There
must be good stuff in the British Merchant Marine, I felt. Hearts of
oak.

Dinner, which followed the introduction, revealed the Battler rather

as a capable trencherman than as a sparkling conversationalist. His
long reach enabled him to grab salt, potatoes, pepper, and other
necessaries without the necessity of asking for them; and on other
topics he seemed to possess no views which he deemed worthy of
exploitation. A strong, silent man.

That there was a softer side to his character was, however, made
clear to me when, after smoking one of my cigars and talking for
awhile of this and that, Ukridge went out on one of those mysterious
errands of his which were always summoning him at all hours and
left my guest and myself alone together. After a bare half-hour’s
silence, broken only by the soothing gurgle of his pipe, the coming
champion cocked an intimidating eye at me and spoke.

“You ever been in love, mister?”

I was thrilled and flattered. Something in my appearance, I told

myself, some nebulous something that showed me a man of
sentiment and sympathy, had appealed to this man, and he was
about to pour out his heart in intimate confession. I said yes, I had
been in love many times. I went on to speak of love as a noble
emotion of which no man need be ashamed. I spoke at length and
with fervour.

“R!” said Battling Billson.

 Then, as if aware that he had been chattering in an undignified
manner to a comparative stranger, he withdrew into the silence
again and did not emerge till it was time to go to bed, when he said
“Good night, mister,” and disappeared. It was disappointing.
Significant, perhaps, the conversation had been, but I had been
rather hoping for something which could have been built up into a
human document, entitled “The Soul of the Abysmal Brute,” and sold
to some editor for that real money which was always so badly
needed in the home.

Ukridge and his protégé left next morning for Barnes, and, as that
riverside resort was somewhat off my beat, I saw no more of the
Battler until the fateful night at Wonderland. From time to time
Ukridge would drop in at my rooms to purloin cigars and socks, and
on these occasions he always spoke with the greatest confidence of
his man’s prospects. At first, it seemed, there had been a little
difficulty owing to the other’s rooted idea that plug tobacco was an
indispensable adjunct to training: but towards the end of the first
week the arguments of wisdom had prevailed and he had consented
to abandon smoking until after his début. By this concession the
issue seemed to Ukridge to have been sealed as a certainty, and he
was in sunny mood as he borrowed the money from me to pay our
fares to the Underground station at which the pilgrim alights who
wishes to visit that Mecca of East-end boxing, Wonderland.

The Battler had preceded us, and when we arrived was in the
dressing-room, stripped to a breath-taking semi-nudity. I had not
supposed that it was possible for a man to be larger than was Mr.
Billson when arrayed for the street, but in trunks and boxing shoes
he looked like his big brother. Muscles resembling the hawsers of an
Atlantic liner coiled down his arms and rippled along his massive
shoulders. He seemed to dwarf altogether the by no means flimsy
athlete who passed out of the room as we came in.

“That’s the bloke,” announced Mr. Billson, jerking his red head
after this person.
 We understood him to imply that the other was his opponent, and
the spirit of confidence which had animated us waxed considerably.
Where six of the pick of the Merchant Marine had failed, this stripling
could scarcely hope to succeed.

“I been talkin’ to ’im,” said Battling Billson.

I took this unwonted garrulity to be due to a slight nervousness

natural at such a moment.

“’E’s ’ad a lot of trouble, that bloke,” said the Battler.

The obvious reply was that he was now going to have a lot more,
but before either of us could make it a hoarse voice announced that
Squiffy and the Toff had completed their three-round bout and that
the stage now waited for our nominee. We hurried to our seats. The
necessity of taking a look at our man in his dressing-room had
deprived us of the pleasure of witnessing the passage of arms
between Squiffy and the Toff, but I gathered that it must have been
lively and full of entertainment, for the audience seemed in excellent
humour. All those who were not too busy eating jellied eels were
babbling happily or whistling between their fingers to friends in
distant parts of the hall. As Mr. Billson climbed into the ring in all the
glory of his red hair and jumping muscles, the babble rose to a roar.
It was plain that Wonderland had stamped our Battler with its
approval on sight.

The audiences which support Wonderland are not disdainful of

science. Neat footwork wins their commendation, and a skilful
ducking of the head is greeted with knowing applause. But what
they esteem most highly is the punch. And one sight of Battling
Billson seemed to tell them that here was the Punch personified.
They sent the fighters off to a howl of ecstasy, and settled back in
their seats to enjoy the pure pleasure of seeing two of their fellow-
men hitting each other very hard and often.

The howl died away.

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