Alwyn G. Davies Organotin Chemistry OrganotinChemistry,SecondEdition.AlwynG.Davies Copyright2004Wiley-VCHVerlagGmbH&Co.KGaA. ISBN:3-527-31023-1 Further Titles of Interest H. Yamamoto, K. Oshima (Eds.) Main Group Metals in Organic Synthesis Two Volume Set 2004, ISBN 3-527-30508-4 N. Auner, J. Weis (Eds.) Organonsilicon Chemistry V From Molecules to Materials 2003, ISBN 3-527-30670-6 B. Rieger, L. S. Baugh, S. Kacker, S. Striegler (Eds.) Late Transition Metal Polymerization Catalysis 2003, ISBN 3-527-30435-5 I. Marek (Ed.) Titanium and Zirconium in Organic Synthesis with a foreword of V. Snieckus 2002, ISBN 3-527-30428-2 B. Cornils, W. A. Herrmann (Eds.) Applied Homogeneous Catalysis with Organometallic Compounds A Comprehensive Handbook in Three Volumes 2002, ISBN 3-527-30434-7 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