Organotin Chemistry, Second Edition

436 Pages·2004·17.083 MB·English

by  Prof. Alwyn G. Davies(auth.)

Alwyn G. Davies
Organotin Chemistry
OrganotinChemistry,SecondEdition.AlwynG.Davies
Copyright2004Wiley-VCHVerlagGmbH&Co.KGaA.
ISBN:3-527-31023-1
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Alwyn G. Davies
Organotin Chemistry
Second, Completely Revised
and Updated Edition
WILEY-VCH Verlag GmbH & Co. KGaA
Prof. Alwyn G. Davies
University College London
Department of Chemistry
20 Gordon Street
London WC1H 0AJ
Great Britain
This book and theaccompanging disk were carefully produced. Nevertheless, author and publisher
do not warrant the information contained therein to be free of errors. Readers are advised to keep in
mind that statements, data, illustrations, procedural details or other items may inadvertently be inac-
curate.
Library of Congress Card No. applied for.
British Library Cataloguing-in-Publication Data: A catalogue record for this book is available
for the British Library
Die Deutsche Bibliothek – CIP Cataloguing-in-Publication-Data: A cataloguerecord for this publication
is available from Die Deutsche Bibliothek
The cover picture of a double-ladder tetraorganodistannoxane and its solid state 119Sn NMR spectrum
was kindly provided by Jens Beckmann and Dainis Dakternieks of Deakin University.
© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Printed on acid-free and chlorine-free paper
All rights (including those of translation into other languages). Nopart of this book may be reproduced
in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a
machine language without written permission from the publishers. Registered names, trademarks, etc.
used in this book, even when not specificallymarked as such, are not to be considered unprotected by
law.
Composition: Druckhaus »Thomas Müntzer«, 99947 Bad Langensalza
Printing: Strauss Offsetdruck GmbH, Mörlenbach
Bookbinding: Großbuchbinderei J. Schäffer GmbH & Co. KG, Grünstadt
Printed in the Federal Republic of Germany.
ISBN 3-527-31023-1
Preface
Organotin compounds have been claimed to have been studied by more techniques, and
to have found more applications, than the organic derivatives of any other metal. This
has resulted in an extensive literature that continues to grow at an ever-increasing rate,
and provides the justification for this second edition of OrganotinChemistry.
I have again tried to provide an analysis of and guide to that literature. Some chapters
have simply been revised and brought up to date, but most have been completely rewrit-
ten, and new sections have been added. Publications are covered up to the beginning of
2003.
This account is supplemented by the literature database on the accompanying CD,
which I hope readers will use to find their way around the organotin literature and to
counteract the severe compression and selection that is necessary in a book of this size.
Further details are given below.
I am very grateful to Peter Smith (UCL) and Fred Armitage (KCL) who read all of
the text, and to Mike Lappert, David Cardin, and Gerry Lawless (University of Sussex),
Dainis Dakternieks, Andrew Duthie, and Jens Beckmann (Deakin University), and Sarah
Wilsey (ICL) who read selected chapters. Peter Smith, Fred Armitage, and Sarah Wilsey
also helped to check the proofs. They did much to reduce the numbers of errors and
omissions, and to improve the text, but I would appreciate any comments from readers
on the book or on the database. My thanks are also due to Gudrun Walter (Wiley-VCH)
who saw the book through to publication, and to my wife for all help non-chemical.
The Organotin Database
The accompanying CD carries a database of more than 5,500 references on which this
book is based, but only a fraction of which appear in the text. It is in the form of an

EndNote library (2Edtinlib.enl) and of a tagged text file in Refer format (2Edtinlib.txt).
Each reference carries details of the author, title, and journal, and also keywords,
usually a brief abstract, and always a note of the relevant section or sections in the book.
For example, references to papers on compounds containing a tin-silicon bond can be
retrieved by searching for the keyword SnSi or the section number 19.5.0.0. Further
details are given on the files readme.txt and keywords.txt on the CD.
The text file can be read on any word-processor and searched in the usual way, and it
can also be imported into other reference-managing programs (Refer, BibIX, ProCite,
Reference Manager, etc). The EndNote library provides more flexibility than the textfile:
the individual fields (author, title, abstract, keywords, notes etc.) can be searched and
edited, and the program also automatically compiles the bibliography of a paper. A dem-
onstration program can be downloaded fromwww.endnote.co.uk.
November 2003 Alwyn Davies
Chemistry Department,
University College,
20 Gordon Street,
London WC1H 0AJ, UK
[email protected]
Contents vii
Contents
1 Introduction 1
1.1 History 1
1.2 Nomenclature 3
1.3 Overview of Synthesis 4
1.4 Overview of Structures 6
1.5 Bibliography 8
2 Physical Methods and Physical Data 13
2.1 Physical Methods 13
2.1.1 Infrared and Raman Spectroscopy 13
2.1.2 Mössbauer Spectroscopy 14
2.1.3 Mass Spectrometry 16
2.1.4 NMR Spectroscopy 18
2.1.5 Photoelectron Spectroscopy 25
2.2 Physical Data 26
3 The Stannyl Group as a Substituent 31
3.1 Tin as a Hydrogen Equivalent 31
3.1.1 Chemical Reactions 35
3.1.2 C-Sn Hyperconjugation 36
3.1.2.1 Carbon Radicals 36
3.1.2.2 Carbon Cations: the β-Tin Effect 36
3.1.2.3 Filled π-Systems 39
3.1.2.4 Carbon Cations: the γ-, δ-, and ε-Effects 41
3.2 Stannyl Substituent Constants 41
3.2.1 Electronic Effects 41
3.2.2 Steric Effects 42
4 Formation of the Carbon-Tin Bond 45
4.1 The Reaction of Organometallic Reagents with Tin Compounds 45
4.2 The Reaction of Stannylmetallic Compounds with Organic
Electrophiles 49
4.3 The Reaction of Tin or Tin(II) Compounds with Alkyl Halides 51
4.4 The Hydrostannation of Alkenes and Alkynes 54
4.5 Metallostannation of Alkenes and Alkynes 59
4.6 The Reaction of Acidic Hydrocarbons with Sn-O and Sn-N Bonded
Compounds 60
4.7 Carbonyl-forming Eliminations 61
5 Alkylstannanes 67
5.1 Structures and Properties 67
5.2 Mechanisms of Cleavage 70
5.3 Reactions 72
5.3.1 With Protic Acids 72
viii Contents
5.3.2 With Halogens 73
5.3.3 With Lewis Acids 74
5.3.4 With Sulfur Dioxide 75
5.3.5 Tin/Lithium Transmetallation 75
5.3.6 With Free Radicals 75
5.3.7 By Electron Transfer 76
5.3.8 With Peroxides 78
5.4 Fluorous Alkylstannanes 78
6 Functionally-substituted Alkylstannanes 82
6.1 α-Halogenoalkylstannanes 82
6.2 Other α-Substituted Alkylstannanes 84
6.3 β-Functional Alkylstannanes 92
6.4 γ-Functional Alkylstannanes 94
7 Aryl- and Heteroaryl-stannanes 100
7.1 Arylstannanes 100
7.2 The Stannylium Ion and the Wheland Intermediate 105
7.3 Heteroarylstannanes 107
8 Alkenyl- and Alkynyl-stannanes, and Stannacyclopentadienes 114
8.1 Alkenyl-tin Compounds 114
8.1.1 Formation 114
8.1.2 Reactions 121
8.2 Alkynyltin Compounds 123
8.2.1 Formation 123
8.2.2 Reactions 125
8.3 Stannacyclopentadienes 128
9 Allyl-, Allenyl-, Propargyl, and Cyclopentadienyl-stannanes 133
9.1 Allylstannanes 133
9.1.1 Formation 133
9.1.2 Properties 135
9.1.3 Reactions 136
9.1.3.1 Transmetallations 136
9.1.3.2 Reaction with Electrophiles 137
9.1.3.3 Reactions with Radicals 139
9.1.3.4 Ene reactions 140
9.2 Allenyl- and Propargyl-stannanes 142
9.2.1 Preparation 142
9.2.2 Reactions 143
9.3 Cyclopentadienylstannanes 144
9.3.1 Formation 144
9.3.2 Properties 145
9.3.3 Reactions 147
9.3.4 Stannylmetallocenes 148
10 Stannacycloalkanes 156
10.1 Monostannacycloalkanes, R2Sn(CH2)n 156
10.2 Stannacyclopentadienes 159
10.3 Oligostannacycloalkanes, [R2Sn(CH2)n]m 160
Contents ix
10.3.1 Formation 160
10.3.2 Structures and Properties 162
11 Organotin Halides 166
11.1 Preparation 166
11.1.1 The Reaction of RM with SnX4 166
11.1.2 The Kocheshkov Reaction 167
11.1.3 Preparation from Organotin Oxides or Hydroxides 168
11.1.4 Exchange of Anionic Groups at Tin 169
11.1.5 The Reactions of Halogens with Sn-Sn Bonded Compounds 170
11.2 Physical Properties and Structures 171
11.3 Coordination Complexes 174
11.4 Reactions 175
12 Organotin Hydroxides and Oxides 179
12.1 Triorganotin Hydroxides and Oxides 179
12.1.1 Preparation and Properties 179
12.1.2 Reactions 182
12.2 Diorganotin Hydroxides and Oxides 185
12.3 Monoorganotin Hydroxides and Oxides 193
12.4 Stannametalloxanes 195
13 Organotin Carboxylates and Other Oxyesters. Stannylium Ions 203
13.1 Organotin Carboxylates 203
13.1.1 Preparation 203
13.1.2 Structures 205
13.1.3 Properties 207
13.2 Carbonates and Carbamates 208
13.3 Derivatives of Phosphorus Acids 209
13.4 Organotin Derivatives of Other Oxyacids and of Thioacids 210
14 Organotin Alkoxides, Phenoxides, and Peroxides 214
14.1 Acyclic Alkoxides and Phenoxides 214
14.1.1 Preparation 214
14.1.2 Structures and Properties 218
14.1.3 Reactions 219
14.2 1,3,2-Dioxastannacycloalkanes 223
14.2.1 Formation 223
14.2.2 Structures and Properties 224
14.3 Acyclic Organotin Enolates 228
14.3.1 Preparation 229
14.3.2 Reactions 230
14.4 1,3,2-Dioxastannolenes 233
14.5 Organotin Peroxides 234
15 Organotin Hydrides 244
15.1 Preparation 244
15.1.1 Reductions with Metal Hydrides 244
15.1.2 Decarboxylation of Stannyl Formates 246
15.1.3 Hydrolysis of Stannylmetallic Compounds 247
15.1.4 Alkylation of R2SnHM 247
x Contents
15.1.5 Special Hydrides 248
15.2 Properties 249
15.3 Reactions 251
15.3.1 Reactions with Protic Acids and Carbenium ions. 252
15.3.2 Reactions with Metal Halides 253
15.3.3 Reactions with Strong Bases 253
15.3.4 Reactions Leading to the Formation of Sn-Sn Bonds 253
15.3.5 Radical Reactions 255
15.3.5.1 Reactions of Radicals with Tin Hydrides 256
15.3.5.2 Reduction of Halides 257
15.3.5.3 Reduction of Thiocarbonyl Compounds 259
15.3.5.4 Reduction of Other Substrates 259
16 Compounds with Sn-N Bonds 266
16.1 Aminostannanes 266
16.1.1 Preparation 266
16.1.1.1 Transmetallation 266
16.1.1.2 Transamination 267
16.1.1.3 Addition to Multiple Bonds 268
16.1.1.4 Ene Reactions 268
16.1.1.5 Miscellaneous Methods 269
16.1.2 Structures 269
16.1.3 Reactions 270
16.1.3.1 With Protic Acids 270
16.1.3.2 With Metal Derivatives 271
16.1.3.3 With Other Singly-bonded Electrophiles 272
16.1.3.4 With Doubly-bonded Electrophiles 273
16.2 Stannyl Porphyrins and Corroles 274
16.3 Amidostannanes 275
16.4 Sulfonamidostannanes 276
16.5 Stannaimines, R2Sn=NR′ 277
16.6 Compounds with Sn–P Bonds 278
17 Compounds with Sn-S Bonds 283
17.1 Organotin Sulfides 283
17.1.1 Preparation 283
17.1.2 Structures 285
17.1.3 Reactions 286
17.2 Stannathiones R2Sn=S 287
17.3 Organotin Thiolates RnSn(SR′)4-n 287
18 Compounds with Sn-Sn Bonds 292
18.1 Introduction 292
18.2 Acyclic Distannanes 292
18.2.1 Formation 292
18.2.1.1 From a Stannylmetallic Compound and a Halide RnSnX4-n 292
18.2.1.2 From an Organotin Compound RnSnX4-n and a Metal 293
18.2.1.3 From an Organotin Hydride RnSnH4-n and a compound RnSnX4-n 294
18.2.1.4 By Elimination of Dihydrogen from an Organotin Hydride 295
18.2.1.5 By Insertion of a Stannylene R2Sn: into an SnM Bond 296
18.2.1.6 By Abstraction of a Hydrogen Atom from R3SnH 296
Contents xi
18.2.1.7 By Cathodic Reduction of R3SnX 296
18.2.2 Structures 297
18.2.3 Properties 297
18.3 Linear Oligostannanes 301
18.4 Cyclic Oligostannanes 303
19 Compounds with Tin-metal Bonds 311
19.1 Alkali Metals 311
19.1.1 Formation 311
19.1.2 Properties 313
19.1.3 Structures 313
19.1.4 Reactions 314
– +
19.1.5 Pentaorganostannates R5Sn Li 315
19.2 Magnesium 316
19.3 Calcium, Strontium, and Barium 317
19.4 Boron and Aluminium 317
19.5 Silicon, Germanium, and Lead 319
19.6 Copper 321
19.7 Zinc, Cadmium, and Mercury 322
19.8 Platinum and Palladium 323
19.9 Other Transition Metals 327
20 Organotin Radicals and Radical Ions 333
•
20.1 Organotin Radicals R3Sn 333
20.1.1 Generation 333
20.1.2 ESR Spectra 338
20.1.3 Reactions 339
•
20.2 Stannylalkyl Radicals R3SnCn 343
•+
20.3 Radical Cations RnSnX4-n 344
•− •−
20.4 Radical Anions RnSnX4-n and R2Sn 346
21 Stannylenes, Distannenes, and Stannenes 351
21.1 σ-Bonded Stannylenes 351
21.1.1 Transient Stannylenes 351
21.1.2 Persistent Stannylenes 353
21.2 Distannenes 359
21.3 Distannynes 360
21.4 Stannenes and Heterostannenes 361
21.5 π-Bonded Stannylenes 363
22 Organic Synthesis: Tin/Lithium Transmetallation,
the Stille Reaction, and the Removal of Tin Residues 373
22.1 Tin/Lithium Transmetallation 373
22.2 Stille Coupling Reactions 375
22.3 The Removal of Tin Residues 378
23 Applications, Environmental Issues, and Analysis 383
23.1 Applications 383
23.2 Environmental Issues 387
23.3 Analysis 388
Author Index 391
Subject Index 421