Organosilicon Chemistry – From Molecules to Materials

Norbert Auner, Johann Weis3-527-30670-6

Table of contents :
Cover Page……Page 1
Title: Organosilicon Chemistry V – From Molecules to Materials……Page 4
ISBN 3527306706……Page 5
Preface……Page 6
Acknowledgments……Page 8
Contents (with page links)……Page 9
Introduction: Organosilicon Chemistry – Facts and Perspectives……Page 18
Reactions of Silicon Atoms – an Access to Unusual Molecules……Page 22
Reactions of Silicon Atoms with Methane and Mane in Solid Argon: A Matrix Spectroscopic Study……Page 28
Cryogenic Trapping Reactions of Silicon Atoms: New Insights into the Photochemistry of Complexes of Silicon Atoms with Donor Molecules……Page 32
New Reactions of Stable Silylenes……Page 36
Insertion Reactions of the Stable Silylene Si[(NCH2tBu)2C6H4-1,2]……Page 44
A Model System for the Generation of Silyl Cationic Species of Different Reactivity and Stability……Page 51
Synthesis and Chemistry of Some Bridged Silicocations……Page 62
New Donor-Stabilized Organosilicon Cations: Synthesis, Structure and Reactivity……Page 67
Novel Pentacoordinate Siliconium Complexes Stabilized by Oxygen and Nitrogen Donors: Highly Sensitive and Unusual Equilibrium between Ionic Penta- and Neutral Hexacoordinate Compounds……Page 72
Binuclear Ethylene-Bridged Silicon Chelates: Equilibrium between Neutral Hexacoordinate and Ionic Pentacoordinate Siliconium Complexes……Page 78
Bonding in Silicon Compounds – Long-Range Si/N Interactions in Organosilicon Molecules and Molecular Cations……Page 83
Thermolytic Formation and Trapping of Silenes Strongly Influenced by Reversed Polarization……Page 95
Synthesis, Structure and Reactivity of Intramolecularly Donor-Stabilized Silenes……Page 99
Cyclotrimetallenes Consisting of Heavier Group 14 Elements: A New Unsaturated Small Ring System……Page 109
On the Way to a Disilyne RSiSiR……Page 118
From Silylenes and Disilenes to a Tetrasilabuta-1,3-diene and Related Compounds……Page 131
The Formation of a Solid from the Reaction SiCl4(g) + O2(g) == SiO2(s) + 2 Cl2(g)……Page 143
Stepwise Formation of Si-O Networks by Means of Hydrolysis/Condensation……Page 147
The Conformational Preference of the Methyl Group in 1-Methyl-1-silacyclohexane……Page 152
Origin of Photoluminescence in Organosilicon Compounds Containing Styrene Subunits……Page 156
Photoluminescence Characteristics of Linear Methy- land Phenyl- Substituted Siloxanes……Page 162
Syntheses of Silyllithium Reagents Starting from Tetraorganosilanes……Page 167
Selective Transformations Starting from a Diastereomerically Enriched Lithiated Benzylsilane……Page 172
Synthesis of a Highly Enantiomerically Enriched Silyllithium Compound……Page 184
Alkynylsilyl Anions – Versatile Building Blocks for Silicon-Containing Polymers……Page 188
Reactions of Trimethylsiloxychlorosilanes (Me3SiO)RPhSiCl (R = H, Me, Et, iPr, tBu, Ph, Mes) with Lithium Formation and Reactivity of Trimethylsiloxysilyllithiums……Page 192
Silacyclobutanes: Head-to-Head Dimerization Versus Anionic Polymerization α-Silyl Substituted Carbanions as Reactive Intermediates……Page 197
Polysilylanions – Easily Available Building Blocks for the Synthesis of Oligosilyl Transition Metal Compounds……Page 203
Experimental Determination of the Inversion Barriers of Oligosilyl Anions……Page 207
Regiospecific and Enantioselective Polymerization to Poly [(dibutylamino)( trimethyldisilene)] by the Masked Disilene Method……Page 212
The Cationic Rearrangement of (3-Hydroxy-1-propenyl)tris(trimethylsilyl)silanes into (1-Trimethylsilyl-2-propenyl)-bis(trimethylsilyl)silanols……Page 219
Chiral β-Silyl Aldehydes as Precursors of Chiral β-Hydroxy Acids and Chiral 1,3-Diols……Page 224
Revisiting the Si2Cl6 Cleavage of Group 14 Element Phosphanes: Phosphane-Catalyzed Rearrangements……Page 227
Some New Nucleophile-Induced Reactions Involving SiCl2, GeCl2 and GeMe2 Transfer……Page 230
Synthesis, Structure and Reactivity of Novel Oligosilyl Anions……Page 234
Synthesis of SiH2-Containing Polymers Using Silyl Triflate Intermediates……Page 239
Silicon Compounds with Geminal Donor Centers……Page 243
Cyclic Silylhydrazines – Synthesis, Isomerizations, and Quantum Chemical Calculations……Page 250
Silylhydroxylamines – Synthesis, Isomerisation, and Quantum Chemical Calculations……Page 263
SiO and SiOSiN Chains, Rings and Cages……Page 271
Isomeric Cyclosilazanes and their Application as Precursors for Silicon-Based Ceramics……Page 278
Silicon and Germanium Compounds with Amidinate Ligands……Page 287
Development of Force Field Parameters for Amino-Substituted Organodisilanes……Page 294
Novel Cyclic and Polycyclic Chalcogenides of Silicon……Page 299
Hypersilylchalcogenolate Derivates of Group 14 Elements……Page 305
Syntheses and Properties of Novel Cage-Shaped Molecules Containing an Extended Silicon Backbone……Page 311
Synthesis and Reactivity of Novel Tin-Modified Oligosilanes……Page 316
Mutual Effects between the Trialkylsilyl Substituents and the MmPn, Cages of Phosphanediides (M = Mg, Ca, Sr, Ba, and Sn)……Page 320
Differing Affinities of the Triorganylsilyl and -stannyl Substituents for Oxygen or Nitrogen, and Phosphorus, Respectively……Page 324
Mono- and Oligosilanes with Pyrazole Ligands……Page 329
A New Type of Silicon Complex with Salen-Type Ligands……Page 334
Gas-Phase Reactions of Free Methyl Cations with Amines and Their Organosilicon Analogues: A Radiochemical Study……Page 338
Calculation of 29Si Chemical Shifts Using a Density-Functional Based Tight-Binding Scheme……Page 341
29Si NMR Chemical Shifts of Four- and Five-Membered Organosilacycles: Experimental and Theoretical Studies……Page 346
29Si NMR Chemical Shifts of Siloxanes: Ab Initio and Density Functional Study……Page 351
Domain Size Determination of Poly(phthalamide)/Poly(dimethylsiloxane) Block Copolymers by 1H Solid-state Spin Diffusion NMR Spectroscopy……Page 356
Esterification Study of Acetoxysilane by Alcohols and Phenols……Page 361
Organosilicon Compounds in Medicine and Cosmetics……Page 365
Synthesis and Biological Activity of Silocanyl- and Silatranylmethyl Ethers of Acrylic Acids……Page 369
Biodegradability and Silatrane Effect Mechanism……Page 373
Intensification of Unsaturated Organomagnesium Chloride Production Reaction……Page 377
Silylative Coupling and Cross-Metathesis of Alkenes and Dienes with Vinyl-Silicon Derivatives – New Catalytic Routes to Synthesis of Organosilicon Compounds……Page 380
Thermolytic Formation and Trapping of Silenes Strongly Influenced by Reversed Polarization……Page 392
Tailoring Properties of Silicon-Containing Oxide Catalysts via the Thermolytic Molecular Precursor Route……Page 396
Organosilicon Chemistry and Nanosciences……Page 406
Catalytic Activity of Rhodium-Siloxide Complexes in Hydrosilylation of Allyl Ethers and Allyl Esters……Page 432
Synthesis and Complex Chemistry of Novel Di- and Trihydroxyoligosilanes……Page 437
Thioether Functionalized Octasilsesquioxanes……Page 442
Synthesis of Cyclopentadienyl-Substituted Polyhedral Zirconasiloxanes……Page 446
Preparation of Highly Porous Silicates by Fast Gelation of H-Silsesquioxane……Page 452
Metal Complexes Containing Extended-Reach Siloxypyridine and Related Ligands……Page 464
Agostic versus Hypervalent Si-H Interactions in Half-Sandwich Complexes of Nb and Ta……Page 468
The Reactivity of Platinum Complexes Containing Hemilabile Ligands Towards Silanes and Stannanes……Page 473
57Fe-Moessbauer Spectra and X-ray Structures of Dipolar Ferrocenylhexasilanes……Page 479
Dipolar 1,2-N,N-Dimethylaminomethylferrocenyl Complexes for Nonlinear Optics?……Page 484
Metallo-silanols – Precursors for the Generation of Novel Metallo-siloxanes and Metalloheterosiloxanes……Page 490
Half-Sandwich Complexes of Iron and Tungsten with Silanol-Functionalized Cyclopentadienyl Ligand……Page 503
Synthesis and Electrochemical Properties of Silanes with Iron-Containing Donors……Page 507
Sustainable Silicon Production……Page 512
Reactivity of Doped Silicon in the Direct Synthesis of Methylchlorosilanes……Page 526
Solvent Role in the Triethoxysilane Direct Process……Page 531
Methylsilane Production by Means of Methyldiethoxysilane Catalytic Disproportionation……Page 535
Investigations of the Reactivity of Methylchloro- and Methylaminodisilanes toward Alkenes……Page 539
New Organofunctional Silanes for Adhesives, Sealants and Spray Foams……Page 544
Isocyanatopropyltrimethoxysilane – Key Intermediate of New Silane Coupling Agents……Page 553
Development of Adhesion Promoters on the Basis of Secondary Reactions of Carbofunctional Organosilicon Monomers……Page 558
Synthesis of Chiral Amino-Substituted Organosilanes……Page 562
Water-Borne Fluoroalkylsilanes: a New Family of Products for Surface Modification……Page 568
Mineral-Filled Thermoplastics: How Silanes Make the Difference……Page 574
The Role of Silanes in Filled and Crosslinked Polymers……Page 579
Hybrid Coatings Based on Silanes: Precursor Methods to Make Hybrid Organic-Inorganic Coatings……Page 590
Marketable Products Based on Secondary Raw Materials from Organosilicon Production Facilities……Page 598
Correlation of the Viscosity and the Molecular Weight of Silicone Oils with the T2 NMR Relaxation Times……Page 601
Oligoethylsiloxane Modification……Page 612
Comblike Oligosiloxanes with Higher N-Alkyl Substituents – A Basis for Lubricants of the New Century……Page 617
Permeability of Silicone-Water Interfaces in Water-in-Oil Emulsions……Page 623
New Textile Softener, Rhodorsil Hydrosoft……Page 629
Nature Meets Silicones – Synthesis and Properties of Modern Organomodified Silicones……Page 639
Organo-Modified Hydropolysiloxanes for Release Control in Silicone Paper Coatings……Page 649
Catalytic Hydrosilylation of Fatty Compounds……Page 655
Polycarbosilanes as Precursors of Novel Membrane Materials……Page 658
Innovative Hybrid Coatings for Façades……Page 662
Adhesion of Silicone Coatings to Plastic Films……Page 667
Thermoplastic Silicone Elastomers……Page 676
LC Silicones Improving the Temperature-Dependent Optical Performance of STN Displays……Page 681
Self-Adhesive Liquid Silicone Rubbers (LSRs) for the Injection Molding of Rigid Flexible Combinations……Page 688
Oil-Bleeding Properties of Self-Lubricating Liquid Silicone Rubbers……Page 695
PDMS-b-PEO Block Copolymers as Surfactants in the Synthesis of Mesostructured Silica: A Theoretical and Practical Approach……Page 706
Preparation and Properties of Porous Hybrids Silicone Resin for Interlayer Dielectronic Application……Page 713
Control of the Dispersion of Metal Oxide Phases in Silica Gels via Organically Modified Alkoxysilanes……Page 717
Interaction of Silica Particles in a Model Rubber System: The Role of Silane Surface Treatments……Page 722
The Structure of a PDMS Layer Grafted onto a Silica Surface Studied by Means of DSC and Solid-state NMR……Page 732
Novel Routes for the Preparation of Nanoporous Silica Particles……Page 753
Particle Size Distribution of Fumed Silica Agglomerates at Low Shear Stress……Page 758
Hydroxylation of Amorphous Fumed Silicas Demonstrated by IGC, Solid-state NMR and IR Spectroscopies……Page 764
Fumed Silica – Rheological Additive for Adhesives, Resins, and Paints……Page 769
Morphology of Toner-Silica Interfaces……Page 784
Selective Surface Deposition of Colloidal Particles……Page 789
Synthesis and Functionalization of Monodisperse Nanoparticles with High Optical Density Based on Inorganic Networks……Page 802
Oxidation States of Si and Ge Sheet Polymers……Page 806
Light-Emitting Properties of Size-Selected Silicon Nanoparticles……Page 814
Spinel-SiAlONs A New Group of Silicon-Based Hard Materials……Page 825
Aluminosiloxanes as Molecular Models for Aluminosilicates……Page 831
Investigation of Silicone-Modified Photocatalytic TiO2 Formation by Solid-Liquid Reaction and Its Structural Changes under Irradiation……Page 836
Author Index (with page links)……Page 844
Subject Index (with page links)……Page 850
Back Page……Page 856