Chemistry of Inorganic Ring Systems (eBook)

Front 
1 
The Chemistry of Inorganic Ring Systems 4
Copyright Page 5
Table of Contents 12
Preface 6
List of Contributors 8
Chapter 1. CLUSTERS, CAGES AND CONCATENATIONS 24
1. Introduction 24
2. Mechanisms of Borane Cluster Formation 25
3. Synthesis of New Cluster Types 28
4. Fluxional Cluster Isomerism 33
5. Acknowledgements 35
6. References 35
Chapter 2. NOVEL DELOCALIZED RINGS INVOLVING HEAVIER MAIN GROUP ELEMENTS 38
1. Introduction 38
2. Synthesis of Novel Potentially Delocalized Rings 41
3. Structures and Properties 41
4. Rings Comprised of Heavier Main Group Elements Only 43
5. Conclusion 46
6. Acknowledgement 46
7. References 46
Chapter 3. BINARY CARBON SULFIDES: UNUSUAL MOLECULES AND MATERIALS 48
1. Introduction 48
2. Background 49
3. Anionic Carbon Sulfides 49
4. Molecular, Binary Carbon Sulfides 51
5. Reactivity of Carbon Sulfides 55
6. Summary and Outlook 55
7. Acknowledgment 56
8. References 56
Chapter 4. NOVEL SILICON RING COMPOUNDS FROM DISILENES 58
1. Reactions with Chalcogens 59
2. Reaction with Dioxygen 61
3. Reaction with Nitro- and Nitrosobenzene 63
4. Reactions with Azides and Azobenzene 64
5. Reactions with Phosphorus 67
6. Reaction with Bis(Phosphine)Platinum 71
7. Summary 71
8. Acknowledgements 71
9. References 72
Chapter 5. NOVEL RING SYSTEMS FROM CYCLOTRISILANES AND CYCLOTRISTANNANES 74
1. Introduction 74
2. Synthesis and Reactivity of Cyclotrisilanes 75
3. Synthesis and Reactivity of Cyclotrigermanes 87
4. Synthesis and Reactivity of Cyclotristannanes 89
5. References 94
Chapter 6. HOMO- AND HETEROCYCLIC Si-O-SYSTEMS -RINGS AND CAGES 98
1. Bifunctional Silanols - Initial Chemical Reagents of Siloxane Synthesis 100
2. Alkali Metal Derivatives of Monomeric Silanols 101
3. Ring Precursors and Ring Systems 107
4. Summary 122
5. References 122
Chapter 7. EXOTIC POLYHEDRAL OLIGOGERMANES AND RELATED MOLECULES 124
1. Hexakis(trimethylsilyl) prismane: C6 (SIMe3)6. Synthesis of Hexakis (trimethylsilyl) tetracyclo [2.2.0.02'6.0 '5] hexane 126
2. Hexagermaprismane: Ge6[CH (SIMe3)2]6.Synthesis of Tetracyclo [2.2.0.02'6.03'5 ] hexagermane 130
3. Octagermacubane: Ge8[(CMeEt2 )]8.Synthesis of Pentacyclo [4.2.0.02'50.'03'8'07'7] octagermane 133
4. Tetrahalogenocyclotetragermane:A Potential Precursor of Cage and Ladder Systems 134
5. Cage and Ladder Polygermanes:Synthesis of Tetracyclo[3.3.0.02'7.03'6] octagermane andTricyclo[4.2.0.02'5]octagermane 136
6. One Pot Synthesis of Oligogermanes 141
7. Acknowledegment 145
8. References 146
Chapter 8. NEW HETEROMETALLIC SILYLAMIDES WITH POLYCYCLIC AND CAGE-LIKE STRUCTURES 148
1. Introduction 148
2. Syntheses of Heterometallic Octamethyltrisilazyls 149
3. Molecular Structures of Heterometallic Octamethyltrisilazyls in the Solid 151
4. General Discussion of the Structural Details in Heterometallic Octamethyltrisilazyls 160
5. Acknowledgements 166
6. References 166
Chapter 9. STRAINED INORGANIC HETEROCYCLIC COMPOUNDS AND THEIR CONVERSION TO MACROCYCLES AND HIGH POLYMERS 168
1. The Importance of Ring-Opening Polymerization and Ring Expansion Reactions 168
2. Ring Opening Polymerization of Chlorocyclophosphazenes: The Classical Route to Poly(organophosphazenes) 169
3. Extension of the Ring-Opening Polymerization Process to other Cyclophosphazenes 172
4. Cyclophosphazenes that Resist Polymerization 174
5. Cyclic Trimers that Bear Both Halogeno- and Organic Side Groups 177
6. Two Possible Mechanisms 182
7. Effect of Ring Strain Induced by Transannular Structures 184
8. Ring Strain Generated by the Presence of Heteroelements 186
9. General Implications for the Future 188
10. Acknowledgements 188
11. References 188
Chapter 10. INORGANIC RINGS ON CARBON CHAINS 194
1. Introduction 194
2. Co- and Homopolymerizations Reactions 196
3. Reactions of Inorganic Rings on Carbon Chains 208
4. Acknowledgements 212
5. References 212
Chapter 11. Pn AND Asn UNITS AS BUILDING BLOCKS FOR METALLACYCLES, CAGES, SANDWICH AND TRIPLE-DECKER COMPLEXES 216
1. Introduction 216
2. Results 217
3. References 229
Chapter 12. PHOSPHORUS-CONTUNING MACROCYCLES. A GAME OF BUILDING BLOCKS 232
1. Introduction 232
2. Macrocycles Arising from [2 + 2]Cyclocondensations 234
3. Macrocycles Arising from [1 + 1]Cyclocondensations 240
4. Macrocycles Arising from [3 + 3]Cyclocondensations 246
5. Functionalized Macrocycles 247
6. Conclusion 252
7. Acknowledgements 253
8. References 253
Chapter 13. THE SYNTHESIS OF SULFUR- AND SELENIUM-CONTUNING ORGANIC AND INORGANIC RINGS FROM TITANOCENE PRECURSORS 256
1. Introduction 256
2. Sulfur Homocycles 257
3. Cyclic Organic Polysulfanes 260
4. Silicon- and Germanium-Containing Cyclo Polysulfanes 264
5. Phosphorus- and Arsenic-Containing Polysulfanes 265
6. Selenium Homocycles 266
7. Selenium-Containing Heterocycles 267
8. Conclusions and Outlook 271
9. References 273
Chapter 14. SYMBIOSIS BETWEEN MAIN GROUP AND TRANSITION ELEMENTS 278
1. Introduction 278
2. Examples for Metal Containing S-N-Rings 279
3. S-N Heterocycles with Sulfur Atoms of Coordination Number 4 279
4. S-N-O Heterocycles 281
5. From Acyclic to Cyclic CSN Compounds 282
6. P-S-N Metal Compounds 284
7. Metal Containing P-N Heterocycles 286
8. Metallacyclosiloxanes 289
9. Metal Containing Boron-Nitrogen Heterocycles 291
10. Prospects 291
11. Acknowledgement 292
12. References 292
Chapter 15. DIPHOSPHADITHIA- AND DIPHOSPHADISELENA-TETRAZOCINES AND THEIR S(Se),S'(Se')-DIALKYL(ARYL)DERIVATIVES 294
1. Introduction 294
2. Synthetic Methods 295
3. X-Ray Structures 297
4. Electronic Structures 298
5. 31P NMR Spectroscopic Data 299
6. Structural Isomers of 1,5-Diphosphadithiatetrazocines 300
7. Comparison of Sulfur- and Selenium-Containing Rings 301
8. Oxidative-Addition Reactions 303
9. Coordination Chemistry 303
10. Formation of Anions 311
11. Polymerization 314
12. Concluding Remarks 314
13. Acknowledgements 314
14. References 316
Chapter 16. HETEROCYCLIC THIAZYL AND SELENAZYL RADICALS SYNTHESIS AND APPLICATIONS IN SOLID STATE ARCHITECTURE
1. Introduction 318
2. Heterocyclic Radical Anions 320
3. Neutral Heterocyclic Radicals 321
4. Neutral TT-Radicals as Molecular Conductors 330
5. Summary 339
6. References 339
Chapter 17. SOME SYNTHETIC AND STRUCTURAL ASPECTS OF DITHIADIAZOLES, RCN2S2, AND RELATED COMPOUNDS 346
1. Introduction 346
2. Nomenclature 349
3. Synthesis of RCNSSN+ Salts 349
4. Synthesis of RCNSNS+ Salts and the SNS+ Synthon 350
5. PhCNSSN+ Salts Hydrolysis, Metathesis and Charge-Transfer Salts
6. Dithiadiazoles: Synthesis and Structure 356
7. Reactions of Dithiadiazoles 360
8. Conclusion 368
9. Acknowledgements 368
10. References 369
Chapter 18. THE PREPARATION AND STRUCTURE OF METALLASULFUR/SELENIUM NITROGEN COMPLEXES AND CAGES 372
1. Introduction 372
2. Thionitrosyl Complexes 373
3. Diimide and NSO- Complexes 374
4. S2N2 Complexes 378
5. MS2N2 and Related Isoelectronic Rings 380
6. Six Membered Rings - MS2N3 and MS3N2 387
7. Other Complexes 389
8. Conclusion 391
9. References 392
Chapter 19. HOMOPOLYATOMIC SELENIUM CATIONS AND RELATED HALOPOLYSELENIUM CATIONS 396
1. Introduction 396
2. The Energetics of Homopolyatomic Selenium Cation and lodo-Polyselenium Cation Formation 399
3. Se42+ 401
4. I2Se+SeSeSe+I2 403
5. Se6IMF6 (M = As, Sb) 405
6. Se6I2(AsF6)2.2SO2(s) 408
7. Se7+SeSeCl and Br2Se+SeSeBr 414
8. Se102+ 415
9. Se82+ and Se2I42+ 418
10. The Highly p -Bonded S2I42+ 424
11. Conclusions 427
12. Acknowledgements 428
13. References 429
Chapter 20. BINARY SELENIUM-NITROGEN SPECIES AND RELATED COMPOUNDS 432
1. Introduction - Scope of Review 433
2. Neutral Selenium Nitrides and Related Species 433
3. Selenium-Nitrogen Cations and Related Species 438
4. Selenium-Nitrogen Anions and Related Species 444
5. Conclusions - Future Developments 446
6. Acknowledgements 447
7. References 447
Chapter 21. COMPLEXES INVOLVING INORGANIC AROMATIC RINGS 452
1. Introduction 452
2. Transition Metal Complexes 454
3. Molecular Orbital Calculations 457
4. Qualitative MO Model 461
5. Summary 470
6. References 471
Chapter 22. COMMENTS ON THE NOMENCLATURE OF INORGANIC RING SYSTEMS 474
1. Introduction 474
2. Defining the Inorganic Ring Concept 474
3. Current Procedures of Naming Inorganic Rings 475
4. New CNIC Proposals 479
5. A Rational Nomenclature System Based upon the Nodal Concept 480
6. Concluding Remarks 489
7. References 490
8. Appendix 491
SUBJECT INDEX 502