Steudel The Chemistry of Inorganic Ring Systems

1. Auflage 2013
ISBN: 978-1-4832-9115-4
Verlag: Elsevier Science & Techn.
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, Band Volume 14, 509 Seiten, Web PDF

Reihe: Studies in Inorganic Chemistry

The present volume considers the most recent developments in the chemistry of cyclic inorganic and organoelement compounds. Nineteen of the 22 chapters are based on invited and other lectures presented at the 6th International Symposium on Inorganic Ring Systems held in Berlin on August 18-22, 1991.Main group compounds dominate the content from boron via carbon, silicon, germanium, tin, nitrogen, phosphorus and arsenic, to sulfur and selenium. The book is organized by element, moving from left to right in the main groups of the Periodic Table, followed by one chapter each on bonding and nomenclature of ring molecules. The list of contributors comprises distinguished scientists from 8 countries.

Autoren/Hrsg.

Steudel, R.

Inhaltsverzeichnis

1;Front
Cover;1
2;The Chemistry of Inorganic Ring Systems;4
3;Copyright Page;5
4;Table of Contents;12
5;Preface;6
6;List of Contributors;8
7;Chapter 1. CLUSTERS, CAGES AND CONCATENATIONS;24
7.1;1. Introduction;24
7.2;2. Mechanisms of Borane Cluster Formation;25
7.3;3. Synthesis of New Cluster Types;28
7.4;4. Fluxional Cluster Isomerism;33
7.5;5. Acknowledgements;35
7.6;6. References;35
8;Chapter 2. NOVEL DELOCALIZED RINGS INVOLVING HEAVIER MAIN GROUP ELEMENTS;38
8.1;1. Introduction;38
8.2;2. Synthesis of Novel Potentially Delocalized Rings;41
8.3;3. Structures and Properties;41
8.4;4. Rings Comprised of Heavier Main Group Elements Only;43
8.5;5. Conclusion;46
8.6;6. Acknowledgement;46
8.7;7. References;46
9;Chapter 3. BINARY CARBON SULFIDES: UNUSUAL MOLECULES AND MATERIALS;48
9.1;1. Introduction;48
9.2;2. Background;49
9.3;3. Anionic Carbon Sulfides;49
9.4;4. Molecular, Binary Carbon Sulfides;51
9.5;5. Reactivity of Carbon Sulfides;55
9.6;6. Summary and Outlook;55
9.7;7. Acknowledgment;56
9.8;8. References;56
10;Chapter 4. NOVEL SILICON RING COMPOUNDS FROM DISILENES;58
10.1;1. Reactions with Chalcogens;59
10.2;2. Reaction with Dioxygen;61
10.3;3. Reaction with Nitro- and Nitrosobenzene;63
10.4;4. Reactions with Azides and Azobenzene;64
10.5;5. Reactions with Phosphorus;67
10.6;6. Reaction with Bis(Phosphine)Platinum;71
10.7;7. Summary;71
10.8;8. Acknowledgements;71
10.9;9. References;72
11;Chapter 5. NOVEL RING SYSTEMS FROM CYCLOTRISILANES AND CYCLOTRISTANNANES;74
11.1;1. Introduction;74
11.2;2. Synthesis and Reactivity of Cyclotrisilanes;75
11.3;3. Synthesis and Reactivity of Cyclotrigermanes;87
11.4;4. Synthesis and Reactivity of Cyclotristannanes;89
11.5;5. References;94
12;Chapter 6. HOMO- AND HETEROCYCLIC Si-O-SYSTEMS -RINGS AND CAGES;98
12.1;1. Bifunctional Silanols - Initial Chemical Reagents of Siloxane Synthesis;100
12.2;2. Alkali Metal Derivatives of Monomeric Silanols;101
12.3;3. Ring Precursors and Ring Systems;107
12.4;4. Summary;122
12.5;5. References;122
13;Chapter 7. EXOTIC POLYHEDRAL OLIGOGERMANES AND RELATED MOLECULES;124
13.1;1. Hexakis(trimethylsilyl) prismane: C6 (SIMe3)6. Synthesis of Hexakis (trimethylsilyl) tetracyclo [2.2.0.02'6.0 '5] hexane;126
13.2;2. Hexagermaprismane: Ge6[CH (SIMe3)2]6.Synthesis of Tetracyclo [2.2.0.02'6.03'5 ] hexagermane;130
13.3;3. Octagermacubane: Ge8[(CMeEt2 )]8.Synthesis of Pentacyclo [4.2.0.02'50.'03'8'07'7] octagermane;133
13.4;4. Tetrahalogenocyclotetragermane:A Potential Precursor of Cage and Ladder Systems;134
13.5;5. Cage and Ladder Polygermanes:Synthesis of Tetracyclo[3.3.0.02'7.03'6] octagermane andTricyclo[4.2.0.02'5]octagermane;136
13.6;6. One Pot Synthesis of Oligogermanes;141
13.7;7. Acknowledegment;145
13.8;8. References;146
14;Chapter 8. NEW HETEROMETALLIC SILYLAMIDES WITH POLYCYCLIC AND CAGE-LIKE STRUCTURES;148
14.1;1. Introduction;148
14.2;2. Syntheses of Heterometallic Octamethyltrisilazyls;149
14.3;3. Molecular Structures of Heterometallic Octamethyltrisilazyls in the Solid;151
14.4;4. General Discussion of the Structural Details in Heterometallic Octamethyltrisilazyls;160
14.5;5. Acknowledgements;166
14.6;6. References;166
15;Chapter 9. STRAINED INORGANIC HETEROCYCLIC COMPOUNDS AND THEIR CONVERSION TO MACROCYCLES AND HIGH POLYMERS;168
15.1;1. The Importance of Ring-Opening Polymerization and Ring Expansion Reactions;168
15.2;2. Ring Opening Polymerization of Chlorocyclophosphazenes: The Classical Route to Poly(organophosphazenes);169
15.3;3. Extension of the Ring-Opening Polymerization Process to other Cyclophosphazenes;172
15.4;4. Cyclophosphazenes that Resist Polymerization;174
15.5;5. Cyclic Trimers that Bear Both Halogeno- and Organic Side Groups;177
15.6;6. Two Possible Mechanisms;182
15.7;7. Effect of Ring Strain Induced by Transannular Structures;184
15.8;8. Ring Strain Generated by the Presence of Heteroelements;186
15.9;9. General Implications for the Future;188
15.10;10. Acknowledgements;188
15.11;11. References;188
16;Chapter 10. INORGANIC RINGS ON CARBON CHAINS;194
16.1;1. Introduction;194
16.2;2. Co- and Homopolymerizations Reactions;196
16.3;3. Reactions of Inorganic Rings on Carbon Chains;208
16.4;4. Acknowledgements;212
16.5;5. References;212
17;Chapter 11. Pn AND Asn UNITS AS BUILDING BLOCKS FOR METALLACYCLES, CAGES, SANDWICH AND TRIPLE-DECKER COMPLEXES;216
17.1;1. Introduction;216
17.2;2. Results;217
17.3;3. References;229
18;Chapter 12. PHOSPHORUS-CONTUNING MACROCYCLES. A GAME OF BUILDING BLOCKS;232
18.1;1. Introduction;232
18.2;2. Macrocycles Arising from [2 + 2]Cyclocondensations;234
18.3;3. Macrocycles Arising from [1 + 1]Cyclocondensations;240
18.4;4. Macrocycles Arising from [3 + 3]Cyclocondensations;246
18.5;5. Functionalized Macrocycles;247
18.6;6. Conclusion;252
18.7;7. Acknowledgements;253
18.8;8. References;253
19;Chapter 13. THE SYNTHESIS OF SULFUR- AND SELENIUM-CONTUNING ORGANIC AND INORGANIC RINGS FROM TITANOCENE PRECURSORS;256
19.1;1. Introduction;256
19.2;2. Sulfur Homocycles;257
19.3;3. Cyclic Organic Polysulfanes;260
19.4;4. Silicon- and Germanium-Containing Cyclo Polysulfanes;264
19.5;5. Phosphorus- and Arsenic-Containing Polysulfanes;265
19.6;6. Selenium Homocycles;266
19.7;7. Selenium-Containing Heterocycles;267
19.8;8. Conclusions and Outlook;271
19.9;9. References;273
20;Chapter 14. SYMBIOSIS BETWEEN MAIN GROUP AND TRANSITION ELEMENTS;278
20.1;1. Introduction;278
20.2;2. Examples for Metal Containing S-N-Rings;279
20.3;3. S-N Heterocycles with Sulfur Atoms of Coordination Number 4;279
20.4;4. S-N-O Heterocycles;281
20.5;5. From Acyclic to Cyclic CSN Compounds;282
20.6;6. P-S-N Metal Compounds;284
20.7;7. Metal Containing P-N Heterocycles;286
20.8;8. Metallacyclosiloxanes;289
20.9;9. Metal Containing Boron-Nitrogen Heterocycles;291
20.10;10. Prospects;291
20.11;11. Acknowledgement;292
20.12;12. References;292
21;Chapter 15. DIPHOSPHADITHIA- AND DIPHOSPHADISELENA-TETRAZOCINES AND THEIR S(Se),S'(Se')-DIALKYL(ARYL)DERIVATIVES;294
21.1;1. Introduction;294
21.2;2. Synthetic Methods;295
21.3;3. X-Ray Structures;297
21.4;4. Electronic Structures;298
21.5;5. 31P NMR Spectroscopic Data;299
21.6;6. Structural Isomers of 1,5-Diphosphadithiatetrazocines;300
21.7;7. Comparison of Sulfur- and Selenium-Containing Rings;301
21.8;8. Oxidative-Addition Reactions;303
21.9;9. Coordination Chemistry;303
21.10;10. Formation of Anions;311
21.11;11. Polymerization;314
21.12;12. Concluding Remarks;314
21.13;13. Acknowledgements;314
21.14;14. References;316
22;Chapter 16. HETEROCYCLIC THIAZYL AND SELENAZYL RADICALS; SYNTHESIS AND APPLICATIONS IN SOLID STATE ARCHITECTURE;318
22.1;1. Introduction;318
22.2;2. Heterocyclic Radical Anions;320
22.3;3. Neutral Heterocyclic Radicals;321
22.4;4. Neutral TT-Radicals as Molecular Conductors;330
22.5;5. Summary;339
22.6;6. References;339
23;Chapter 17. SOME SYNTHETIC AND STRUCTURAL ASPECTS OF DITHIADIAZOLES, RCN2S2, AND RELATED COMPOUNDS;346
23.1;1. Introduction;346
23.2;2. Nomenclature;349
23.3;3. Synthesis of RCNSSN+ Salts;349
23.4;4. Synthesis of RCNSNS+ Salts and the SNS+ Synthon;350
23.5;5. PhCNSSN+ Salts; Hydrolysis, Metathesis and Charge-Transfer Salts;354
23.6;6. Dithiadiazoles: Synthesis and Structure;356
23.7;7. Reactions of Dithiadiazoles;360
23.8;8. Conclusion;368
23.9;9. Acknowledgements;368
23.10;10. References;369
24;Chapter 18. THE PREPARATION AND STRUCTURE OF METALLASULFUR/SELENIUM NITROGEN COMPLEXES AND CAGES;372
24.1;1. Introduction;372
24.2;2. Thionitrosyl Complexes;373
24.3;3. Diimide and NSO- Complexes;374
24.4;4. S2N2 Complexes;378
24.5;5. MS2N2 and Related Isoelectronic Rings;380
24.6;6. Six Membered Rings - MS2N3 and MS3N2;387
24.7;7. Other Complexes;389
24.8;8. Conclusion;391
24.9;9. References;392
25;Chapter 19. HOMOPOLYATOMIC SELENIUM CATIONS AND RELATED HALOPOLYSELENIUM CATIONS;396
25.1;1. Introduction;396
25.2;2. The Energetics of Homopolyatomic Selenium Cation and lodo-Polyselenium Cation Formation;399
25.3;3. Se42+;401
25.4;4. I2Se+SeSeSe+I2;403
25.5;5. Se6IMF6 (M = As, Sb);405
25.6;6. Se6I2(AsF6)2.2SO2(s);408
25.7;7. Se7+SeSeCl and Br2Se+SeSeBr;414
25.8;8. Se102+;415
25.9;9. Se82+ and Se2I42+;418
25.10;10. The Highly p -Bonded S2I42+;424
25.11;11. Conclusions;427
25.12;12. Acknowledgements;428
25.13;13. References;429
26;Chapter 20. BINARY SELENIUM-NITROGEN SPECIES AND RELATED COMPOUNDS;432
26.1;1. Introduction - Scope of Review;433
26.2;2. Neutral Selenium Nitrides and Related Species;433
26.3;3. Selenium-Nitrogen Cations and Related Species;438
26.4;4. Selenium-Nitrogen Anions and Related Species;444
26.5;5. Conclusions - Future Developments;446
26.6;6. Acknowledgements;447
26.7;7. References;447
27;Chapter 21. COMPLEXES INVOLVING INORGANIC AROMATIC RINGS;452
27.1;1. Introduction;452
27.2;2. Transition Metal Complexes;454
27.3;3. Molecular Orbital Calculations;457
27.4;4. Qualitative MO Model;461
27.5;5. Summary;470
27.6;6. References;471
28;Chapter 22. COMMENTS ON THE NOMENCLATURE OF INORGANIC RING SYSTEMS;474
28.1;1. Introduction;474
28.2;2. Defining the Inorganic Ring Concept;474
28.3;3. Current Procedures of Naming Inorganic Rings;475
28.4;4. New CNIC Proposals;479
28.5;5. A Rational Nomenclature System Based upon the Nodal Concept;480
28.6;6. Concluding Remarks;489
28.7;7. References;490
28.8;8. Appendix;491
29;SUBJECT INDEX;502