Preface ...................................................... xvii
List of Contributors .......................................... xix
1 Introduction and Overview .................................... 1
1.1 Introduction ............................................ 1
Alwyn G. Davies
1.1.1 History, Occurrence, Production, and
Applications ..................................... 1
1.1.2 The Element ...................................... 3
1.1.3 Structure and Bonding ............................ 4
1.1.4 Organotin Compounds, RnSnm ....................... 5
1.1.5 Organotin Compounds With Electronegative
Ligands, RnSnX4-n ................................ 9
1.1.6 Preparation of Organotin(IV) Compounds .......... 10
1.1.7 Preparation of Organotin Compounds in Lower
Valence States .................................. 13
1.1.8 Literature ...................................... 13
References ............................................. 14
2 Fundamentals in Tin Chemistry ............................... 17
2.1 NMR Spectroscopy of Tin Compounds ...................... 17
Bernd Wrackmeyer
2.1.1 Introduction .................................... 17
2.1.2 Experimental .................................... 17
2.1.3 Nuclear Spin Relaxation ......................... 20
2.1.4 Chemical Shifts δ119Sn .......................... 21
2.1.5 Indirect Nuclear Spin-Spin Coupling Constants
nJ (119Sn,X) .................................... 39
References ............................................. 45
2.2 Tin(II) Clusters ....................................... 53
Tristram Chivers and Dana J. Eisler
2.2.1 Introduction ..................................... 53
2.2.2 Imidotin Cubane Clusters ........................ 53
2.2.3 The Seco-Cubane Sn3 (μ3-NtBu)(μ-NtBu)(μ-NtBu)2 .. 60
2.2.4 Double-Cubane Clusters .......................... 61
2.2.5 Imidotin Chalcogenides .......................... 62
2.2.6 Phosphido- and Arsenido-Tin Clusters ............ 65
2.2.7 Summary and Future Prospects .................... 66
References ............................................. 66
2.3 Mono-Organotin Oxo-Clusters ............................ 69
François Ribot
2.3.1 Introduction .................................... 69
2.3.2 Molecular Structures ............................ 70
2.3.3 Syntheses and Formation Mechanisms .............. 78
2.3.4 Conclusions ..................................... 89
Acknowledgments ........................................ 90
References ............................................. 90
2.4 Organotin Carboxylate and Sulfonate Clusters ........... 93
Vadapalli Chandrasekhar, Puja Singh, and Kandasamy
Gopal
2.4.1 Introduction .................................... 93
2.4.2 Organotin Carboxylates .......................... 93
2.4.3 Organotin Sulfonates ........................... 105
2.4.4 Conclusion ..................................... 113
Acknowledgments ....................................... 114
References ............................................ 114
2.5 Macrocyclic and Supramolecular Chemistry of
Organotin(IV) Compounds ............................... 117
Herbert Höpfl
2.5.1 Introduction ................................... 117
2.5.2 Metallosupramolecular Chemistry with Tin ....... 117
2.5.3 Formation of Tin Macrocycles and Extended
Networks ....................................... 120
2.5.4 Conclusions and Perspectives ................... 133
Acknowledgments ....................................... 133
References ............................................ 133
2.6 Deltahedral Zintl Ions of Tin: Synthesis, Structure,
and Reactivity ........................................ 138
Slavi C. Sevov
2.6.1 Introduction ................................... 138
2.6.2 Background ..................................... 138
2.6.3 Geometry, Charge, Electron Count, and
Electronic Structure ........................... 140
2.6.4 Reactions With Nine-Atom Deltahedral Zintl
Anions of Tin .................................. 143
2.6.5 Solution Studies by NMR ........................ 148
2.6.6 Concluding Remarks ............................. 150
Acknowledgments ....................................... 150
References ............................................ 150
2.7 Stable Stannylium Cations in Condensed Phases ......... 152
Joseph B. Lambert
2.7 1 Introduction .................................... 152
2.7.2 Pentacoordination (Trigonal Pyramids) .......... 154
2.7.3 Tetracoordination: Binding with Solvent or
Anion .......................................... 155
2.7.4 Tricoordination: NMR Evidence for Free
Stannylium Ions ................................ 156
2.7.4 Tricoordination: Crystallographic Evidence
and Computational Confirmation of Free
Stannylium Ions ................................ 157
2.7.6 Summary ........................................ 158
References ............................................ 159
2.8 Preparation and Coordination Chemistry of Mono- and
Bidentate Benzannulated N-Heterocyclic Stannylenes
Including Some Germanium and Lead Analogs ............. 160
Alexander V. Zabula and F. Ekkehardt Hahn
2.8.1 Introduction ................................... 160
2.8.2 Stable N-Heterocyclic Stannylenes,
Germylenes, and Plumbylenes .................... 160
2.8.3 Complexes of Bidentate N-Heterocyclic
Germylenes and Stannylenes ..................... 166
References ............................................ 174
2.9 Stannenes, Distannenes, and Stannynes ................. 177
Yoshiyuki Mizuhata and Norihiro Tokitoh
2.9.1 Introduction ................................... 177
2.9.2 Distannenes (Sn=Sn) ............................ 177
2.9.3 Stannenes (Sn=C) ............................... 183
2.9.4 Silastannenes (Si=Sn) and Germastannenes
(Ge=Sn) ........................................ 193
2.9.5 Stannynes (Sn≡C) ............................... 195
2.9.6 Distannynes (Sn≡Sn) and Their Reduced
Species ........................................ 196
References ............................................ 198
2.10 Tetraorganodistannoxanes: Simple Chemistry From
a Personal Perspective ................................ 201
Klaus Jurkschat
2.10.1 Introduction ................................... 201
2.10.2 Unsymmetrically Substituted
Tetraorganodistannoxanes ....................... 202
2.10.3 Looking for the Third Dimension ................ 209
2.10.4 Variation of R ................................. 212
2.10.5 Variation of Spacer Z .......................... 212
2.10.6 Variation of the Electronegative Substituents
X and Y ........................................ 221
2.10.7 Miscellaneous .................................. 221
Acknowledgments ....................................... 229
References ............................................ 229
2.11 Unusual Bonds and Coordination Geometries ............. 231
Mónica Moya-Cabrera, Vojtech Jancik and Raymundo
Cea-Olivares
2.11.1 Introduction ................................... 231
2.11.2 Unusual Bonds .................................. 231
2.11.3 Unusual Coordination Geometries ................ 241
References ............................................ 247
2.12 Tin(II) Heterobimetallic and Oligometallic
Derivatives ........................................... 251
Muhammad Mazhar and Imtiaz-ud-Din
2.12.1 Introduction ................................... 251
2.12.2 General Synthetic Procedures ................... 254
2.12.3 Characterization Techniques .................... 256
2.12.4 Stoichiometric and Structural Aspects of
Tin(II) Heterobimetallic and Oligometallic
Compounds ...................................... 258
2.12.5 Conclusion ..................................... 267
References ............................................ 267
2.13 Computational Methods for Organotin Compounds ......... 269
Sarah R. Whittleton, Russell J. Boyd, and T. Bruce
Grindley
2.13.1 Introduction ................................... 269
2.13.2 Relativistic Effects in Heavy Elements ......... 269
2.13.3 Effective Core Potentials ...................... 270
2.13.4 Other Computational Methods Available for Tin .. 271
2.13.5 Current State of Computational Organotin
Chemistry ...................................... 272
2.13.6 Structure Prediction ........................... 272
2.13.7 Reaction Pathways and Mechanisms ............... 274
2.13.8 Thermochemistry ................................ 276
2.13.9 Bond Strengths and Bond Dissociation
Enthalpies ..................................... 276
2.13.10 Spectroscopic and Related Properties .......... 277
2.13.11 Conclusion .................................... 278
Acknowledgments ....................................... 278
References ............................................ 279
3 Materials Chemistry and Structural Chemistry of Tin
Compounds .................................................. 285
3.1 Tin Compounds For CVD (Chemical Vapor Deposition) ..... 285
Geraldo M. de Lima
3.1.1 Introduction ................................... 285
3.1.2 General Aspects of CVD ......................... 285
3.1.3 Organometallic Chemical Vapor Deposition
(MOCVD) ........................................ 287
3.1.4 Tin Compounds For CVD .......................... 287
3.1.5 Tin(IV) Oxide and Related Materials ............ 287
3.1.6 Tin Sulfides ................................... 290
3.1.7 Tin(II) Selenide and Telluride ................. 291
3.1.8 Tin (IV) Phosphide ............................. 292
3.1.9 Tin Alloys ..................................... 292
3.1.10 Summary ........................................ 292
References ............................................ 293
3.2 Class II Tin-Based Hybrid Materials Prepared From
Alkynyltin Precursors ................................. 296
Thierry Toupance
3.2.1 Introduction ................................... 296
3.2.2 Functionalization of Oxide Surfaces ............ 297
3.2.3 Self-Assembled Tin-Based Hybrid Materials ...... 301
3.2.4 Nanoporous Nanostructured Tin Dioxide
Materials ...................................... 306
3.2.5 Conclusion ..................................... 309
Acknowledgments ....................................... 310
References ............................................ 310
3.3 Organotin Compounds as PVC Stabilizers ................ 312
Esen Arkis
3.3.1 Introduction ................................... 312
3.3.2 Types of Organotin Stabilizers ................. 313
3.3.3 Tin Carboxylates ............................... 314
3.3.4 Tin Mercaptides ................................ 315
3.3.5 The Mechanism of Stabilization ................. 315
3.3.6 Operational Considerations ..................... 317
3.3.7 Evaluating Stability ........................... 320
3.3.8 Conclusion ..................................... 322
References ............................................ 323
3.4 Organotin Compounds as Anion-Selective Carriers in
Chemical Sensors ...................................... 324
Nikos Chaniotakis
3.4.1 Introduction to Chemical Sensors ............... 324
3.4.2 Potentiometrie Ion Selective Electrodes
(ISEs) ......................................... 324
3.4.3 The Ionophores ................................. 326
3.4.4 Organotin-Mediated Anion Partitioning into
Liquid Polymeric Membranes ..................... 326
3.4.5 Anion Selective Organotin-based ISEs ........... 329
3.4.6 Conclusions .................................... 336
3.5 Tin Compounds as Flame Retardants and Smoke
Suppressants .......................................... 339
Paul A. Cusack
3.5.1 Introduction ................................... 339
3.5.2 Tin Treatments For Fibers ...................... 339
3.5.3 Zinc Stannates ................................. 340
3.5.4 Recent Developments ............................ 343
3.5.5 Fire-Retardant Mechanism ....................... 346
3.5.6 Summary ........................................ 348
References ............................................ 348
3.6 Quadratic Non-Linear Optical Properties of Tin-
Based Coordination Compounds .......................... 351
Pascal G. Lacroix and Norberto Farfán
3.6.1 Introduction ................................... 351
3.6.2 Basic Concepts of Quadratic Non-Linear
Optics ......................................... 351
3.6.3 Tin-Based Materials in Quadratic Non-Linear
Optics ......................................... 352
3.6.4 Concluding Remarks ............................. 358
Acknowledgments ....................................... 359
References ............................................ 359
3.7 Monoorganotin Precursors For Hybrid Materials ......... 361
Bernard Jousseaume
3.7.1 Introduction ................................... 361
3.7.2 Functional Trialkynylorganotins ................ 361
3.7.3 Bridged Ditins ................................. 368
3.7.4 Conclusion ..................................... 374
Acknowledgments ....................................... 374
References ............................................ 374
3.8 Organotin Polymers and Related Materials .............. 376
Hemant K. Sharma and Keith H. Pannell
3.8.1 Introduction ................................... 376
3.8.2 Synthesis of Linear Oligostannanes ............. 376
3.8.3 Synthesis of Polystannanes ..................... 378
3.8.4 Properties of Polystannanes .................... 381
3.8.5 Polymers with Tin in the Backbone .............. 386
3.8.6 Polymers with Tin as а Pendant Group ............ 388
Acknowledgments ....................................... 389
References ............................................ 389
3.9 Intermolecular Tin... π-Aryl Interactions: fact or
artifact? A New Bonding Motif For Supramolecular
Self-Assembly in Organotin Compounds .................. 392
Ionel Haiduc, Edward R.T. Tiekink, and Julio
Zukerman-Schpector
3.9.1 Introduction ................................... 392
3.9.2 Discussion ..................................... 393
3.9.3 Conclusions and Outlook ........................ 409
Acknowledgments ....................................... 409
References ............................................ 409
4 Medicinal/Biocidal Applications of Tin Compounds and
Environmental Aspects ...................................... 413
4.1 The Cardiovascular Activity of Organotin Compounds .... 413
Mala Nath
4.1.1 Introduction ................................... 413
4.1.2 Cardiovascular Activity of Organotin
Compounds ...................................... 414
4.1.3 Conclusion ..................................... 425
References ............................................ 427
4.2 Organotins: Insecticidal/Larvicidal Activities and
Quantitative Structure-Activity Relationships ......... 430
George Eng and Xueqing Song
4.2.1 Overview: Organotins ........................... 430
4.2.2 Larvicidal/Insecticidal Activities ............. 430
4.2.3 Quantitative Structure-Activity
Relationships .................................. 435
4.2.4 Food For Thought ............................... 439
References ............................................ 439
4.3 Anti-Fungal Activity of Organotin Compounds ........... 443
Heloisa Beraldo and Geraldo M. de Lima
4.3.1 Introduction ................................... 443
4.3.2 Biological Applications of Organotin
Compounds ...................................... 443
4.3.3 Fungi and Fungal Infections .................... 443
4.3.4 Mechanisms of Biological Action of Organotin
Compounds ...................................... 444
4.3.5 Structure-Activity Relationships ............... 445
4.3.6 Anti-Fungal Screening .......................... 446
4.3.7 Conclusions .................................... 452
References ............................................ 452
4.4 Chemical and Biotechnological Developments in
Organotin Cancer Chemotherapy ......................... 454
Claudio Pettinari and Fabio Marchetti
4.4.1 Introduction ................................... 454
4.4.2 Developments in the Design of Organotin Anti-
Cancer Compounds ............................... 455
4.4.3 Conclusion ..................................... 465
References ............................................ 465
4.5 Impact of Organotin Compounds on the Function of
Human Natural Killer Cells ............................ 469
Margaret M. Whalen
4.5.1 Introduction .................................... 469
4.5.2 Effects of n-butyltin Chlorides on Human NK
Cell Function: Tri-n-Butyltin Chloride
(TBTC) ......................................... 470
4.5.3 Di-n-Butyltin Chloride (DBTC) .................. 472
4.5.4 Effects of Trimethyltin Chloride (TMTC) on
Human NK Cell Function ......................... 474
4.5.5 Effects of Dimethylphenyltin Chloride (DMPTC)
on Human NK Cell Function ...................... 475
4.5.6 Effects of Methyldiphenyltin Chloride (MDPTC)
on Human NK Cell Function ...................... 475
4.5.7 Effects of Triphenyltin Chloride (TPTC) on
Human NK Cell Function ......................... 476
4.5.8 Summary ........................................ 477
References ............................................ 479
4.6 Biological Aspects of Organotins: Perspectives in
Structural and Molecular Biology ...................... 482
Hiram I. Beltrán, Rosa Santillan and Norberto Farfán
4.6.1 Introduction ................................... 482
4.6.2 Interaction of Organotin Compounds with
Biological Systems and Mimic Xenobiotics ....... 482
4.6.3 Interaction of Organotin Compounds in Real
and Model Membranes ............................ 484
4.6.4 Roles of Organotin Compounds in Cell
Function ....................................... 488
4.6.5 Aspects of Organotins in Structural and
Molecular Biology .............................. 491
4.6.6 Perspectives ................................... 492
Acknowledgments ....................................... 492
References ............................................ 492
5 Tin in Organic Synthesis ................................... 497
5.1 Applications of Organotin Derivatives for
Carbohydrate Synthesis ................................ 497
T. Bruce Grindley
5.1.1 Introduction ................................... 497
5.1.2 Preparation .................................... 498
5.1.3 Structures ..................................... 500
5.1.4 Reactions ...................................... 504
References ............................................ 512
5.2 Reactions of Se' Substitution for Organostannanes
in Organic Synthesis .................................. 515
David R. Williams, and Partha P. Nag
5.2.1 Introduction ................................... 515
5.2.2 Mechanistic Considerations and a Predictive
Model for Reactions with Aldehydes ............. 516
5.2.3 Allylation Reactions of Substrate Control ...... 519
5.2.4 Allylation Reactions Exhibiting α-Chelation
Control ........................................ 521
5.2.5 Allylation Reactions Exhibiting β-Chelation
Control ........................................ 524
5.2.6 Reactions of γ-(Alkoxy)allylstannanes .......... 526
5.2.7 Reactions of Oxocarbenium Cations .............. 527
5.2.8 Reactions of N-Acyliminium Cations ............. 531
5.2.9 Reactions with α, β-Unsaturated Carbonyl
Compounds ...................................... 532
5.2.10 Reactions of Allylic Stannanes with Imines ..... 533
5.2.11 Transmetalation Reactions of Allylic
Stannanes ...................................... 535
5.2.12 Reactions of Chiral Allylic Stannanes .......... 541
5.2.13 Reactions of Allenylstannanes .................. 543
5.2.14 Transmetalation Reactions of Allenylstannanes .. 547
5.2.15 Reactions of Propargylic Stannaries ............ 550
5.2.16 Enantioselective Reactions with Chiral Lewis
Acids .......................................... 552
5.2.17 Conclusion and Future Outlook .................. 555
References ............................................ 556
5.3 Cross-Coupling of Organotin Compounds for Carbon-
Carbon Bond Formation ................................. 561
Pablo Espinet and Miroslav Genov
5.3.1 Introduction ................................... 561
5.3.2 Mechanistic Aspects and Consequences ........... 561
5.3.3 Catalysts and Ligands .......................... 564
5.3.4 Ligandless Coupling ............................ 570
5.3.5 Copper Effect .................................. 571
5.3.6 Microwave-Assisted Reactions ................... 572
5.3.7 Natural Product Synthesis ...................... 574
5.3.8 Conclusion ..................................... 575
References ............................................ 575
5.4 Stille Cross-Coupling for the Synthesis of Natural
Products .............................................. 579
Sergio Pascual and Antonio M. Echavarren
5.4.1 Introduction ................................... 579
5.4.2 Alkenyl-Alkenyl Stille Coupling ................ 579
5.4.3 Alkenyl-Alkynyl Stille Coupling ................ 587
5.4.4 Alkenyl-Aryl Stille Coupling ................... 587
5.4.5 Aryl-Aryl Stille Coupling ...................... 593
5.4.6 sp3-sp2 Coupling Reactions ..................... 594
5.4.7 Couplings for the Synthesis of Ketones ......... 599
5.4.8 Summary and Outlook ............................ 600
References ............................................ 602
5.5 New Trends in the Synthesis of Solid-Supported
Organotin Reagents and Interest of their Use in
Organic Synthesis in a Concept of Green Chemistry ..... 607
Jean-Mathieu Chrétien, Jeremy D. Kilburn, FranÇoise
Zammattio, Erwan Le Grognec, and Jean-Paul Quintard
5.5.1 Introduction ................................... 607
5.5.2 Removal of Tin Residues by Partition between
Two Phases ..................................... 608
5.5.3 Solid-Supported Organotin Reagents ............. 608
5.5.4 Use of Supported Organotins in Organic
Synthesis ...................................... 613
5.5.5 Perspectives and Conclusions ................... 617
References ............................................ 618
5.6 Palladium-Catalyzed Cascade Cyclization-Anion
Capture Processes Employing Pre- and In Situ-Formed
Organostannanes ....................................... 622
Ron Grigg and Visuvanathar Sridharan
5.6.1 Introduction ................................... 622
5.6.2 Mono-Cyclization-Anion Capture Processes ....... 623
5.6.3 Bis-Cyclization-Anion Capture Processes ........ 630
5.6.4 Cyclization-Anion Capture Processes Involving
Relay Switches ................................. 634
5.6.5 Summary ........................................ 637
References ............................................ 638
5.7 Carbostannylation of Carbon - Carbon Unsaturated
Bonds ................................................. 640
Eiji Shirakawa
5.7.1 Introduction .................................... 640
5.7.3 Carbostannylation of Alkynes ................... 641
5.7.4 Carbostannylation of Alkenes ................... 647
5.7.5 Carbostannylation of Dienes .................... 650
5.7.6 Conclusion ..................................... 651
References ............................................ 651
5.8 Green Organotin Chemistry: an Oxymoron? ............... 653
David Young
5.8.1 Introduction ................................... 653
5.8.2 How Hazardous Are Organostannanes? ............. 654
5.8.3 Removing Organotin By-Products ................. 654
5.8.4 Modified Organotin Reagent for Easy
Separation ..................................... 656
5.8.5 Solid Phase Tin Reagents ....................... 659
5.8.6 Less Toxic Organotin Reagents .................. 661
5.8.7 No-Tin Reagents ................................ 663
5.8.8 Conclusion ..................................... 664
References ............................................ 664
6 Tin in Catalysis ........................................... 667
6.1 Green Organotin Catalysts ............................. 667
Junzo Otera, Monique Biesemans, Vanja Pinoie, Kevin
Poelmans, and Rudolph Willem
6.1.1 Introduction ................................... 667
6.1.2 Fluorous Distannoxane Catalysts ................ 668
6.1.3 Grafted Organotin Catalysts .................... 672
6.1.4 Conclusion ..................................... 678
References ............................................ 678
6.2 Organotin Catalysts for Isocyanate Reactions .......... 681
Werner J. Blank and Edward T. Hessell
6.2.1 Introduction ................................... 681
6.2.2 Mechanism of Urethane Catalysis by Tin
Compounds ...................................... 681
6.2.3 Structure of the Tin Catalyst .................. 681
6.2.4 Mechanisms ..................................... 682
6.2.5 Synergism of Tin Compounds with Amine
Catalysts: DBDTL and l,4-Diazabicyclo[2.2.2]
octane ......................................... 685
6.2.6 Mechanism of Catalysis with Blocked
Isocyanates .................................... 686
6.2.7 Organotin Catalyst Composition ................. 686
6.2.8 Catalysis with Organotin Compounds ............. 687
6.2.9 Applications ................................... 691
6.2.10 Blocked Isocyanates ............................ 694
6.2.11 Catalyst Interactions .......................... 696
6.2.12 Polymer Synthesis .............................. 696
6.2.13 Organotin Replacements ......................... 698
References ............................................ 698
6.3 Catalysis of Reactions of Allyltin Compounds and
Organotin Phenoxides by Lithium Perchlorate ........... 701
Wojciech J. Kinart and Cezary M. Kinart
6.3.1 Catalysis of Metalloene Reactions of
Allylstannanes by Lithium Perchlorate .......... 701
6.3.2 Catalysis of reactions of triorganotin
phenoxides with diethyl azodicarboxylate,
bis(trichloroethyl) azodicarboxylate and
diethyl acetylenedicarboxylate ................. 709
References ............................................ 719
Index ......................................................... 721
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