Organosilicon Chemistry III: From Molecules to 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