Organosilicon Chemistry VI
From Molecules to Materials Volume 1
Edited by Norbert Auner and Johann Weis 7
WILEY- VCH WILEY-VCH Verlag GmbH & Co. KGaA Contents
Introduction Auner, N.; Weis, J.
Chapter I Organosilicon-Based Reactive Intermediates
Learning from Silylenes and Supersilylenes 10 Gaspar, P. P. New Molecular Systems with Silicon-Silicon Multiple Bonds 25 Kira, M; Iwamoto, T.; Ishida, S. l-[2,6-Bis(dimethylaminomethyl)phenyl]-2,2-bis(trimethylsilyl)silenes — Syntheses, Structures, and Reactions 33 Baumer, U.; Reinke, H.; Oehme, H. Quantum Chemical DFT and Experimental Study of oriho-, metha-, and para-Tory 1-Substituted Methylsilene Rearrangements 37 Guselnikov, S. L.; Volkova, V. V.; Avakyan, V. G; Gusel'nikov, L. E. A 1,4-Disilapentalene and a Highly Stable Silicon Diradical 43 Toulokhonova, I.; Stringfellow, T. C; West, R. Kinetic Stabilization of Polysilyl Radicals 48 Kravchenko, V.; Bravo-Zhtvotavskii, D.; Tumanskii, B.; Botoshansky, M.; Segal, N.; Molev, G.; Kosa, M.; Apeloig, Y. Out-of-Range £29Si Chemical Shifts of Diaminosilylenes — an ab initio Study 59 Flock, M.; Dramfeld, A. ' Comparison of Heterocyclic Diaminosilylenes with Their Group 14 Homologs 64 Heinicke, J.; Kuhl, O. Spectroscopic Evidence for the Formation of the Pentamethylcyclopentadienylsilicon Cation 69 Jutzi, P.; Mix, A.; Rumtnel, B.; Neumann, B.; Stammler, H.-G.; Rozhenko, A.; Schoeller, W. W. Synthesis and Characterization of Bissilylated Onium Ions of Group 15 Elements 74 Panisch, R.; Mutter, T. Structural and Spectroscopic Evidence for P-SiC Hyperconjugation in Vinyl Cations 80 Miiller, T.; Juhasz, M; Reed, C. A. Tertiary Trisilyloxonium Ion and Silylenium Cation in Cationic Ring-Opening Polymerization of Cyclic Siloxanes 85 Cypryk, M.; Chojnowski, J.; Kurjata, J.
S: Contents
Chapter II Molecular Inorganic Silicon Chemistry
Dihalodimethylsilanes from Silicon Atoms and Methyl Halides 94 Maier, G.; Glatthaar, J.; Reisenauer, H. P. Reactions of Silicon Atoms with Amines and Phosphine under Matrix Isolation Conditions 101 Maier, G.; Glatthaar, J.; Reisenauer, H. P. New Insights into the Halophilic Reaction of a Stable Silylene with Halocarbons: A Matrix - Spectroscopic Study 107 Glatthaar, J.; Maier, G.; West, R. Compensation Effect in Direct Reactions of Silicon 112 Acker, J.; Lieske, H.; Bohmhammel, K. On Reasons for Selectivity Losses in TCS Synthesis 119 Kurschner, U.; Radnik, J.; Lieske, H; Hesse, K.; Pdtzold, U. Characterization of Trichlorosilane Direct Process Residue 126 Harder, P. J.; Tselepis, A. J.
Dichlorosilylene Transfer Reactions Using Me3GeSiCl3 131 Seppald, E.; Gust, T.; Wismact C; duMont, W.-W. Synthesis of 5-Alkylsilylborazines by Rhodium-Catalyzed Hydroboration of JV-Alkylborazines 136 Lehnert, C; Roewer, G. Hydrosilylation of Ethynylborazines and Their Use for the Formation of a Highly Functionalized Silica Gel 142 Haberecht, J.; Riiegger, H; Nesper, R.; Griitzmacher, H. Influence of the Tri(tert-butyl)silyl Substituents on the Molecular Structures of Phosphanylalanes, -gallanes and -indanes 148 Weinrich, S.; Krofta, M; Schulz, A.; Westerhausen, M. ' Trifluoromethyl Silicon Compounds with Geminal Nitrogen Donor Centers 156 Vojinovic, K.; Mitzel, N. W.; Korth, M; Frohlich, R.; Grimme, S.
Alkali Metal Cyantrimethylsilylamides — M[NCNSi(CH3)3] 160 Kroke, E. Amination in Supercritical Ammonia — Continuous Production of Aminoalkylsilanes 167 Bauer, A.; Weis, J.; Rauch, J. Mono- and Bis(hydroxylamino)silanes — Reactions, Rearrangements, and Structures 170 Ebker, C; Diedrich, F.; Klingebiel, U. From Silyldiamines to Mono-NH-SiF-functional Cyclodisilazanes — Synthesis, Reactions, and Crystal Structures 177 Reiche, C; Klingebiel, U. Contents XI
From Lithium Halogenosilylamides to Four- and/or Fourteen-Membered Rings and New 14n-Electron Systems 182 Wand, A.; Kucharski, S.; Klingebiel, U. Silyl-Enolethers and -Ethers — New Results of Keto-Enol Tautomerism 188 Biischen, T.; Klingebiel, U. "Hypervalent" Molecules — Low-Valency Candidates for Materials? 194 Karsch, H. H; Segmuller, T. Strong Evidence for an Unconventional 1,2-(C-»P)-Silyl Migration: Formation and Reactions ofa/'-SilylPhosphaalkene Complex 202 Ionescu, E; Wilkens, H; Streubel, R. Strong Evidence for an Unconventional 1,2-(C-»P)-Silyl Migration: DFT Structures and Bond Strengths (Compliance Constants) 209 von Frantzius, G.; Grunenberg, J.; Streubel, R. Silyl Group Migrations between Oxygen and Nitrogen in Aminosiloxanes 216 Kliem, S.; Klingebiel, U. Terphenyl Phosphanosilanes 222 Pietschni^ R.; Tirree, J. J. Preparations and X-Ray Structures of some Silicon-Phosphorus and Silicon-Arsenic Cages 228 Hassler, K; Tekautz, G.; Baumgartner, J. Homo- and Heterometallic Bismuth Silanolates 233 Mehring, M.; Mans/eld, D.; Nolde, C; Schumann, M. The Effect of Silyl Anion Substituents on the Stability and NMR Characteristics of Cyclic Polyphosphines — an ab initio/NMR Study 240 Dransfeld, A.; Hassler, K Silanols as Precursors to Cyclo- and Polysiloxanes 245 Veith, M; Rammo, A.; Schutt, F. O.; Spaniol, P. P.; Huch, V. The Origin of Ring Strain and Conformational Flexibility in Tri- and Tetrasiloxane Rings and Their Heavier Group 14 Congeners 252 Beckmann, J.; Dakternieks, D.; him, A. E. K; him, K F.; Jurkschat, K. 29Si NMR Chemical Shift Tensors in Organosilicon Chalcogenides 259 Herzog, U.; Bohme, U.; Brendler, E.
Hypersilyltelluro-Substituted Silanes and (Ph2SiTe)3 265 Lange, H.; Herzog, U.; Roewer, G.; Borrmann, H. Novel Dimeric Pentacoordinate Silicon Complexes: Unusual Reactivity of Electron-Rich Aminosilane Intermediates 271 Dona, N.; Merz, K; Driess, M. Unique Switching of Coordination Number with Imine and Enamine Complexes of Group 14 Elements 279 Wagler, 1; Bohme, U.; Roewer, G. XII Contents
Structures of Novel Diorgano-Substituted Silicon Complexes with Hexacoordinate Silicon Atom 285 Roewer, G.; Wagler, J. Novel Hypercoordinate Silicon Complexes from Silicon Tetrahalides and Bidentate
Chapter in Transition Metals in Organosilicon-Based Chemistry
Transition Metals in Organosilicon Chemistry 382 Tilley, T. D. Hydrosilation (or is it Hydrosilylation?): A Personal Perspective on a Scientifically and Technologically Fascinating Chemical Methodology ....„ 392 Harrod, J. F. DFT Calculations on the Activation of Silanes by Platinum Complexes with Hemilabile P,N Ligands 399 Sturmayr, D.; Schubert, U. Hydrosilylation of Ethylene, Cyclohexene, and Allyl Chloride in the Presence of Pt(O) and Pt(2) Catalysts 404 Chernyshev, E. A.; Belyakova, Z. V.; Knyazev, S. P.; Storozhenko, P. A. Synthesis of Glycidoxypropyl-Silanes and -Siloxanes via Rhodium Siloxide-Catalyzed Hydrosilylation 408 Maciejewski, H; Marciniec, B.; Blazejewska-Chadyniak, P.; Dqbek, I. New Functionalization of Vinyl-Substituted Organosilicon Compounds via Ru-Catalyzed Reactions 416 Marciniec, B.; Itami, Y; Chadyniak, D.; Jankowska, M. Hydrosilylation Using Ionic Liquids 424 Weyershausen, B.; Hell, K; Hesse, U. On-Line FT-Raman Spectroscopy for Process Control of the Hydrosilylation Reaction 432 Baumann, F.; List, T.
[2+2]-Cycloadditions of (OC)4Fe=SiMe2 — Theoretical Study 438 Bohme, U. Reactions of Undecamethylcyclohexasilyl-potassium with-Transition Metal Compounds 445 Hoffmann, F.; Bohme, U.; Roewer, G. Cp-Free Hafnium Silyl Substituted Compounds 452 Frank, D.; Baumgartner, J.; Marschner, C. Metal- and Cyclopentadienyl-Bound Silanol Groups in Tungsten Complexes 457 Bera, H.; Schmitzer, S.; Schumacher, D.; Malisch, W. Half-Sandwich Iron Complexes with a Silanol-Functionalized Cyclopentadienyl Ligand 462 Sohns, A.; Schumacher, D.; Malisch, W.; Nieger, M. Synthesis and Reactivity of Polychlorinated Metallo-Siloxanes 468 Schumacher, D.; Malisch, W.; Soger, N.; Binnewies, M. Half-Sandwich Tungsten Complexes with Silyl-Functionalized r|5-Cyclopentadienyl Ligand 474 Bera, H; Sohns, A.; Malisch, W. XTV Contents
Chapter IV Silicon in Organic and Bioorganic Chemistry
Norbornylsilanes: New Organosilicon Protecting Groups 482 Heldmann, D. K; Stohrer, J.; Zauner, R. Synthesis and Reactivity of an Enantiomerically Pure 7V-Methyl-2-Silyl-Substituted Pyrrolidine „ 488 Strohfeldt, K; Seibel, T.; Wich, P.; Strohmann, C. Diastereomerically Enriched a-Lithiated Benzylsilanes 495 Schildbach, D.; Bindl, M; Hornig, J.; Strohmann, C. An Enantiomerically Enriched Silyllithium Compound and the Stereochemical Course of its Transformations 502 Hornig, J.; Auer, D.; Bindl, M.; Fraafi, V. C; Strohmann C.
Reactions of CF3Si(CH3)3 and C6F5Si(CH3)3 with Perfluoroolefins and Perfluoroimines 508 Nishida, M.; Hayakawa, Y; Ono, T. Bis(trimethylsilyl)mercury: a Powerful Reagent for the Synthesis of Amino Carbenes 515 Otto, M; Rudzevich, V.; Romanenko, V. D.; Bertrand, G. Electrochemical Synthesis of Functional Organosilanes 522 Loidl, B.; Grogger, Ch; Sttiger, H; Pachaly, B.; Weidner, R.; Kammel, T.; Bauer, A. Photoluminfccence and Photochemical Behavior of Silacyclobutenes 527 Yan, D.; Hess, A. A.; Auner, N.; Thomson, M.; Backer M. Tris- and Tetrakis-[oligo(phenylenevinylene)]-silanes: Synthesis and Luminescence Behavior....534 Detert, H; Sugiono, E. Synthesis, Luminescence, and Condensation of Oligo(phenylenevinylene)s with Alkoxysilane End Groups 539 Detert, H; Sugiono, E. How to Make Disilandiyl-Carbon Hybrid Materials: the First ADMET Metathesis Reactions of Organodisilanes 546 Mera, G.; Driess, M. Application of a,co-Bis(dimethylvinylsiloxy)alkanes 553 Pawluc, P.; Gaczewska, B.; Marciniec, B. Synthesis and NMR Spectra of Diaryl- and Dihetarylsilacycloalkanes 559 Ignatovich, L.; Pope Us, J.; Lukevics, E. Synthesis and Biological Activity of Silicon Derivatives of 2-Trifluoroacetylfuran and Their Oximes 563 Ignatovich, L.; Zarina, D.; Shestakova, I.; Germane, S.; Lukevics, E. Silicon Diols, Effective Inhibitors of Human Leucocyte Elastase 569 Showell, G. A.; Montana, J. G; Chadwick, J. A.; Higgs, C; Hunt, H. J.; MacKenzie, R. E; Price, S.; Wilkinson, T. J. Contents XV o Ligands of the l,4'-Silaspiro[tetralin-l,4'-piperidine] Type and the Serotonin/Noradrenaline Reuptake Inhibitor Sila-venlafaxine: Studies on C/Si Bioisosterism 575 Daifi, J. O.; Mutter, B.; Burschka, C; Tacke, R; Bains, W.; Warneck, J. Possible Mechanisms of the Stimulating Effects of Isopropoxygermatran and 1-Ethoxysilatran in Regenerated Liver 582 Voronkov, M. G.; Muhitdinova, H. N.; Nurbekov, M. K; Rasulov, M. M; D'yakov, V. M. Wound Healing Effects of some Silocanes and Silatranes 588 D'yakov, V. M.; Voronkov, M. G.; Kazimirovskaya, V. B.; Loginov, S. V.; Rasulov, M. M. The Development of Methods of Synthesizing Organic Derivatives of Silicon Based on Biogenic Silica 595 Ubaskina, J.; Ofitserov, Y.
Chapter V Organosilicon Compounds for Industrial Applications
Silicon Science and Technology — an Industrialist's View of the Future 602 White, J. W. The Markets for Silicones 610 De Poortere, M. Synthesis of Organofunctional Polysiloxanes of Various Topologies 620 Chojnowski, J. A Facile Synthetic Route to Phosphazene Base Catalysts and Their Use in Siloxane Synthesis....628 Hupfield, P. C; Surgenor, A. E.; Taylor, R. G. Supramolecular Chemistry and Condensation of 01igosiloxane-a,to-Diols HOSiMe2O(SiPh2O)nSiMe2OH (n = 1 - 4) 635 Beckmann, J.; Dakternieks, D.; Duthie, A.; Foitzik, R. C; Beckmann, J. The Reactivity of Carbofunctional Aminoalkoxysilanes inHydrolytic and Reetherification Reactions 641 Kovyazin, V. A.; Kopylov, V. M.; Nikitin, A. V.; Knyazev, S. P.; Chemyshev, E. A. Study of Octyltriethoxysilane Hydrolytic Polycondensation 646 Plekhanova, N. S.; Kireev, V. V.; Ivanov, V. V.; Kopylov, V. M. A Study of the Dependence of Silicone Compositions on the Initial Structure and Composition ofOligoorganosiloxanes 655 Nanushyan, S. R.; Alekseeva, E. I.; Polivanov, A. N. Study of Rheological Properties of Oligoethylsiloxane-Based Compositions 661 Gureev, A. O.; Koroleva, T. V.; Lotarev, M. B.; Skorokhodov, 1.1.; Chemyshev, E. A. Silacyclobutene-PDMS Copolymers — Siloxanes with Unusual Thermal Behavior 668 Backer, M. W.; Hannington, J. P.; Davies, P. R.; Auner, N. Electrochemically Initiated "Silanone Route" for Functionalization of Siloxanes 675 Keyrouz, R.; Jouikov, V.