Organosilicon chemistry III : from molecules to materials ; [lectures and poster contributions of the III. Münchner Silicontage, held in April 1996

Organosilicon Chemistry at its best ...((kursiv)) Like its two hugely successful predecessors, the third volume again presents the latest developments in a rapidly developing field of industsrial and academic research. The contributions from approx. 80 internationally renowned experts and researchers in this fascinating part of the rapidly growing field of main group chemistry describe current trends in organosilicon chemistry and provide summaries of the latest (1997!) knowledge in this area. To facilitate access to the ongoing research this volume is split into two parts, each with a comprehensive introduction: Part 1: Fascinating Organosilicon Compounds Part 2: Silicon Based Materials Organosilicon Chemistry III: from Molecules to Materials......Page 2 Contents......Page 10 Introduction......Page 30 More Compelling Evidence that Silicon is Better Than Carbon: The Thermal Isomerization of Olefins to Carbenes......Page 46 NMR and Quantum Chemical Characterization of Silicon-Substituted Carbocations......Page 54 Matrix Isolation Studies of the Reactions of Silicon Atoms......Page 60 Cycloaddition Reactions of Dimethylaminomethylsilylene with Dienes and Heterodienes......Page 65 Do Unsubstituted Silacyclobutadienes Exist?......Page 68 A Thermally Stable Silylene: Reactivity of the Bis(amino)silylene Si[{N(CH2tBu))2}C6H4-1,2]......Page 73 Pyrido[b]-1,3,2λ2-diazasilole: The First Stable Unsymmetrical Silylene......Page 79 A New Route to Silaheterocycles: Heterobutadiene Cycloaddition......Page 82 Base Coordination: A Way to Nucleophilic Silylenes?......Page 87 Isoelectronic Replacement of Si by P+: A Comparative Study of the Structures of the Spirocyclic EII Compounds E[C(PMe2)2(X)]2 (E = Si, Ge, Sn; X = PMe2,SiMe3) and a Novel Spirocyclic 10 e-Phosphorus Cation(PIII) P[C(PPh2)2(SiMe3)]2+......Page 94 The Main Group Carbonyls RLi-CO and R2Si-CO: An Ab Initio Study......Page 99 Unprecedented Multistep Reactions of Decamethylsilicocene, (Me5C5)2Si:, with CO2, CS2, COS, RNCS (R = Me, Ph), with CF3CCCF3, and with HMn(CO)5......Page 105 Rearrangement of Bis(hypersilyl)silylene and Related Compounds - An Unusual Way to Three-Membered Rings......Page 111 Oxidation of Silenes and Silylenes: Matrix Isolation of Unusual Silicon Species......Page 115 New Silaheterocycles: Formation and Properties......Page 124 Cycloaddition Reactions of 1,1-Dichloro-2-neopentylsilene with Monoterpenes......Page 130 Silaspirocycles as Precursors for a 2-Silaallene......Page 135 Catalytic Carbon-Carbon Hydrogenation of Silicon-Functionalized Olefins......Page 142 Dieno- and Enophilicity of Sila-, Germa-, and Stannaethenes......Page 146 Iminosilanes and Silaamidides: Synthesis and Reactions......Page 149 Metastable Compounds Containing Silicon-Phosphorus and Silicon-Arsenic Multiple Bonds: Syntheses, Structures and Reactivity......Page 155 Silole and Germole Dianions and their Dilithium Derivatives - Are they Aromatic?......Page 173 Supersilylmetal Compounds......Page 181 Trialkylsilyl Substituted Homobimetallic Phosphanides of the Alkaline Earth Metals as well as Zinc......Page 186 The Tris(trimethylsilyl)silyl Substituent: An Old Hat With A New Feather......Page 191 Functionalized Trisilylmethanes and Trisilylsilanes as Precursors of a New Class of Tripodal Amido Ligands......Page 201 Methoxy-bis[tris(trimethylsilyl)silyl]methane: The First Geminal Di(hypersilyl) Compound......Page 207 The Use of the Tris(trimethylsilyl)silyl Group in Stabilization of Low Valent Gallium Compounds......Page 211 Synthesis, Structure, and Reactions of Tris(trimethylsi1yl)silyl Gallanes and Gallates......Page 218 Novel Pathways in the Reactions of Vinylsilanes with Lithium Metal......Page 224 New Organosilicon Reagents: Synthesis, Structure, and Reactivity of (Lithiomethyl)(aminomethyl)silanes......Page 235 (Phenylthiomethyl)silanes as New Bihnctional Assembling Ligands for the Construction of Heterometallic Complexes......Page 240 Synthesis of 1,3-Disilacyclobutanes, 1,3-Digermacyclobutanes, and 1-Germa-3-sila-cyclobutanes with New 1,3-Dimetallated Organoelement Building Blocks......Page 246 Trialkylsilyldiazomethane Derivatives: Wonderful Chemical Building Blocks......Page 252 A New Route to Silaheterocycles: Nucleophilic Aminomethylation......Page 266 Infrared and Raman Spectra, ab initio Calculations, and Rotational Isomerism of Methylated Disilanes......Page 270 1,2-Di-tert-butyltetrafluorodisilane: A Highly Fluxional Molecule......Page 277 Amino-Substituted Disilanes by Reductive Coupling......Page 283 Multifunctional Disilane Derivatives......Page 286 New Transition Metal Substituted Oligosilanes......Page 291 Regiospecific Chlorination and Oxygenation of Pentahydridodisilanyl Complexes of Iron and Ruthenium......Page 296 Inter- and Intramolecular Oxidative Addition of Si-H Bonds......Page 300 Novel Synthetic Approach to Molybdenum-Silicon Compounds: Structures and Reactivities......Page 304 Unexpected Reactivity of Bis-1,2-[(bromodiphenyl)methyl]-1,1,2,2-tetramethyldisilane......Page 310 Trichlorosilane/Triethylamine - An Alternative to Hexachlorodisilane in Reductive Trichlorosilylation Reactions?......Page 315 Disproportionation of Chloromethyldisilanes using Lewis Base Heterogeneous Catalysts -A Way to Influence the Polymer Structure......Page 320 Supersilylated Bromodisilanes, Cyclotri-, and Cyclotetrasilanes......Page 325 Syntheses and 29Si NMR Spectra of Halogenated Trisilanes and Cyclopentasilanes......Page 330 Chlorination of Methylphenyloligosilanes: Products and Reactions......Page 336 Selective Hydrogenation of Methylchlorooligosilanes......Page 341 Electrochemical Formation of Cyclosilanes......Page 346 Undecamethylcyclohexasilanyl Derivatives of Tin(IV) and Lead(IV)......Page 351 New Results in Cyclosilane Chemistry: Siloxene-like Polymers......Page 356 Stepwise Synthesis of Functional Polysilane Dendrimers......Page 362 Synthesis and Reactivity of Novel Polysilynes and Branched Copolysilanes......Page 366 Unusual Polyhedra by Lithiation of Silazanes......Page 371 Isomeric Halosilylhydroxylamines: Preparation and Thermal Rearrangements......Page 377 Reactions of Hydridosilylamides......Page 382 Silylhydrazines: Precursors for Rings, Hydrazones and Pyrazolones......Page 387 Products from Multiple Insertion Reactions between Diisocyanates and Antiheteroaromatic 1,4-Bis(trimethylsilyl)-1,4-dihydropyrazine......Page 393 Some Surprising Chemistry of Sterically Hindered Silanols......Page 398 Silanetriols: Preparation and Their Reactions......Page 405 Silsesquioxanes as Crown Ether Analogs......Page 424 Azomethine-Substituted Organotrialkoxysilanes and Polysiloxanes......Page 429 On the Reaction of (tBu2SnO)3 with Organochlorosilanes. Simple Formation of [(tBu2SnO)2(tBu2SiO)]......Page 432 Silanols and Siloxanes Substituted with the Chiral Iron Fragments Cp(OC)(RPh2P)Fe(R = Ph, (H)(Me)(Ph)C(Me)N) [1]......Page 436 Si-H Functionalized Ferrio-Trisiloxanes C5R5(OC)2Fe–Si(Me)(OSiMe2H)2 (R = H, Me) [1]......Page 441 Novel Siloxy-Bridged Di-, Tri-, and Tetranuclear Metal Complexes from Ferrio- and Tungsten-Silanols......Page 444 The 2-Dimethylaminomethyl-4,6-dimethylphenyl Substituent: A New Intramolecular Coordinating System with High Steric Demand......Page 447 Reaction Behaviour of Hypervalent Silanes......Page 452 Investigations of Nucleophilic Substitution at Silicon: An Unprecedented Equilibrium between an Ionic and a Covalent Chlorosilane......Page 458 Ligand Exchange Mechanism in Novel Hexacoordinate Silicon Complexes......Page 464 Ligand Exchange via Coordinative Si-N Bond Cleavage and Pseudorotation in Neutral Pentacoordinate Silicon Complexes......Page 475 Phosphine Coordination to Silicon Revisited......Page 481 Novel Sila-Phospha-Heterocycles and Hypervalent Silicon Compounds with Phosphorus Donors......Page 489 Germanium Analogues of Zwitterionic Spirocyclic λ5Si-Silicates......Page 495 Introduction......Page 500 The Direct Process to Methylchlorosilanes: Reflections on Chemistry and Process Technology......Page 507 On the Nature of the Active Copper State and on Promoter Action in Rochow Contact Masses......Page 513 On the Acid- and Base-Catalyzed Reactions of Silanediols and Siloxanediols in Water......Page 525 Trace Analysis of Mono- and Trifunctional Groups in Polydimethylsiloxanes Using Reaction Headspace GC......Page 529 Synthesis and Investigation of the Surface Active Properties of New Silane Surfactants......Page 533 Carbohydrate-Modified Siloxane Surfactants: The Effect of Substructures on the Wetting Behaviour on Non Polar Solid Surfaces......Page 539 Synthesis and Application of ω-Epoxy-Functionalized Alkoxysilanes......Page 544 Diffuse Reflectance IR and Time-of-Flight SIMS Investigation of Methoxysilane SA-Layers on Silica and Alumina......Page 549 Ether-Substituted Triethoxy- and Diethoxymethylsilanes: Precursors for Hydrophilic, Elastic Consolidants for Natural Stones......Page 555 Organosilicon Compounds for Stone Impregnation - Long-Term Effectivity and Weathering Stability......Page 560 Studies on the Regioselectivity of the Hydroformylation with Alkenylalkoxysilanes......Page 567 Novel Precursors for Inorganic-Organic Hybrid Materials......Page 572 Mesomorphic Properties of Poly(diphenylsiloxane)......Page 579 Applications of Silicone Elastomers for Electrical and Electronic Fields......Page 584 Cyclic Liquid Crystalline Siloxanes: Chemistry and Applications......Page 595 Modified Polydimethylsiloxanes with Fluorescent Properties......Page 616 Sensitized Cationic Photocrosslinking of α,ω-Terminated Disiloxanes: Cation Formation in Nonpolar Media......Page 623 Cationic Photoinitiators for Curing Epoxy-Modified Silicones......Page 634 Photoconductivity in Polysilylenes: Doping with Electron Acceptors......Page 646 Functionalized Polycarbosilanes as Preceramic Materials......Page 651 Novel Polyorganoborosilazanes for the Synthesis of Ultra-High Thermal Resistant Ceramics......Page 657 Precursors for Silicon-Alloyed Carbon Fibers......Page 661 One-Pot Syntheses of Poly(diorganylsily1ene-co-ethynylene)s......Page 667 Localization Phenomena of Photogenerated Charge Carriers in Silicon Structures: From Organosilicon Compounds to Bulk Silicon......Page 672 Functionalized Structure-Directing Agents for the Direct Synthesis of Nanostructured Materials......Page 678 Novel Aspects of the Chemical Modification of Silica Surface......Page 699 Microporous Thermal Insulation: Theory, Properties, Applications......Page 711 Nitridosilicates - High Temperature Materials with Interesting Properties......Page 720 Author Index......Page 734 Subject Index......Page 740 Edited By Norbert Auner And Johann Weis. Includes Bibliographical References And Indexes.