Stuart Organosilicon Chemistry

Special Lectures Presented at the International Symposium on Organosilicon Chemistry
1. Auflage 2013
ISBN: 978-1-4832-8446-0
Verlag: Elsevier Science & Techn.
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 338 Seiten, Web PDF

Organosilicon Chemistry provides information pertinent to the fundamental aspects and application of organosilicon chemistry. This book discusses the exact manner and extent of d-orbital involvement in organosilicon compounds in ground, electronic, and transition excited states. Organized into two parts encompassing 21 chapters, this book begins with an overview of preparing stable organosiliconium ions. This text then discusses the use of fused salts as reaction media in the preparative chemistry. Other chapters consider a detailed investigation on the molecular association and volatility of alkoxides of group (IV) elements. This book discusses as well the reaction between dimethyldichlorosilane and ethylene glycon, which has been shown to produce a dimeric ten-membered ring compound. The final chapter deals with the results of the investigations concerning the properties of the contact mass and of the non-volatile silicon-free products, which are produced in the direct synthesis of phenylhalogenosilanes. This book is a valuable resource for chemists and research workers.

Dr. Sam Stuart is a physiotherapist and a research Fellow within the Balance Disorders Laboratory, OHSU. His work focuses on vision, cognition and gait in neurological disorders, examining how technology-based interventions influence these factors. He has published extensively in world leading clinical and engineering journals focusing on a broad range of activities such as real-world data analytics, algorithm development for wearable technology and provided expert opinion on technology for concussion assessment for robust player management. He is currently a guest editor for special issues (sports medicine and transcranial direct current stimulation for motor rehabilitation) within Physiological Measurement and Journal of NeuroEngineering and Rehabilitation, respectively.

Autoren/Hrsg.

Stuart, Sam

Inhaltsverzeichnis

1;Front Cover;1
2;Organosilicon
Chemistry;4
3;Copyright Page;5
4;Table of Contents;6
5;FOREWORD;8
6;PART I: PLENARY LECTURES;10
6.1;CHAPTER 1. RECENT ADVANCES ON TWO CLASSICAL PROBLEMS OF ORGANOSILICON
CHEMISTRY;10
6.1.1;I. ORGANOSILICONIUM IONS;10
6.1.2;II. p-BONDING INVOLVING 3d-ORBITALS OF SILICON
IN POLYSILANES;18
6.1.3;CONCLUSION;22
6.1.4;References;22
6.2;CHAPTER 2. ANALOGIEN UND UNTERSCHIEDE ZWISCHEN ORGANOMETALLISCHEN VERBINDUNGEN DES SILIZIUMS, GERMANIUMS UND ZINNS;24
6.2.1;References;42
6.3;CHAPTER 3. SILATRANES: INTRA-COMPLEX HETEROCYCLIC COMPOUNDS OF PENTACOORDINATED SILICON;44
6.3.1;1-ORGANYLSILATRANES;45
6.3.2;1-ORGANOXYSILATRANES;48
6.3.3;KINETICS OF HYDROLYSIS;49
6.3.4;DIPOLE MOMENTS AND THE STRUCTURE OF SILATRANES;52
6.3.5;INFRARED ABSORPTION SPECTRA;56
6.3.6;PROTON MAGNETIC RESONANCE SPECTRA;63
6.3.7;PHYSIOLOGICAL ACTIVITY;65
6.3.8;References;68
6.4;CHAPTER 4. SUR QUELQUES ASPECTS DE LA REACTIVITE DES HYDROGENOSILANES EN CHIMIE ORGANIQUE;72
6.4.1;INTRODUCTION;72
6.4.2;ADDITION D'HYDROGENOSILANES AUX DOUBLES LIAISONS ETHYLENIQUES;72
6.4.3;ACTION DES HYDROGENOSILANES SUR LES CETONES ET LES ALDEHYDES;75
6.4.4;ACTION DES HYDROGENOSILANES SUR LES ACETALS;80
6.4.5;ACTION DES TRIALKYLHYDROGENOSILANES SUR LES NITRILES;82
6.4.6;AMIDES, IMINOETHERS ET IMINES;84
6.4.7;LACTONES;86
6.4.8;LAGT AMES;88
6.4.9;Bibliographie;89
6.5;CHAPTER 5. ÜBER EINIGE HETEROCYCLISCHE RINGSYSTEME DER SILICIUM
CHEMIE;92
6.5.1;References;102
7;PART II: MAIN LECTURES;104
7.1;CHAPTER 6. PREPARATION OF ORGANOSILICON HALIDES IN MOLTEN SALTS AS REACTION MEDIA;104
7.1.1;INTRODUCTION;104
7.1.2;PROPERTIES OF FUSED SALTS;104
7.1.3;APPLICATIONS OF FUSED SALTS;105
7.1.4;References;110
7.2;CHAPTER 7. SPREADING BEHAVIOUR AND ACIDOLYSIS OF THE SILOXANE LINKAGE AS VARYING WITH THE DONOR-ACCEPTOR PROPERTIES OF THE ORGANIC
SUBSTITUENTS;112
7.2.1;SPREADING BEHAVIOUR OF SILOXANES;113
7.2.2;ACIDOLYSIS IN SILOXANES;124
7.2.3;References;127
7.3;CHAPTER 8. SYNTHESIS AND PROPERTIES OF ALKOXY AND ACYLOXYSILANES;128
7.3.1;INTRODUCTION;128
7.3.2;SYNTHESIS OF ALKOXYSILANES;129
7.3.3;PROPERTIES OF ALKOXYSILANES;130
7.3.4;SYNTHESIS OF ACYLOXYSILANES;138
7.3.5;PROPERTIES OF ACYLOXYSILANES;140
7.3.6;DERIVATIVES OF SILICON WITH GLYCOLS;143
7.3.7;DERIVATIVES OF SILICON WITH SALICYLIC AND
a-HYDROXY ACIDS;145
7.3.8;References;146
7.4;CHAPTER 9. SILANE ADDITION REACTIONS—THEIR SYNTHETIC UTILITY AND MECHANISM;150
7.4.1;I. STEREOCHEMISTRY OF SILANE ADDITION REACTIONS;150
7.4.2;2. SYNTHETIC UTILITY OF SILANE ADDITIONS IN RING SYNTHESIS;152
7.4.3;3. MECHANISMS OF SILANE ADDITIONS;152
7.4.4;References;157
7.5;CHAPTER 10. HYDROSILATION IN THE SYNTHESIS OF ORGANOSILANES;158
7.5.1;INTRODUCTION;158
7.5.2;GENERAL RELATIONSHIPS;159
7.5.3;DESCRIPTION BY CATALYST CLASSES;161
7.5.4;MECHANISMS;170
7.5.5;References;172
7.6;CHAPTER 11. STERIC EFFECTS AND p-BONDING IN ORGANOSILICON CHEMISTRY: THEIR ASSESSMENT BY MEANS OF COMPARATIVE ORGANIC CHEMISTRY
OF CARBON AND SILICON;176
7.6.1;I. TRIPHENYLPHOSPHINETRIMETHYLSILYLMETHYLENE;177
7.6.2;II. LITHIUM-INDUCED ISOMERIZATION OF PROPENYLTRIMETHYLSILANE, -GERMANE AND -TIN;180
7.6.3;References;183
7.7;CHAPTER 12. RECENT RESEARCH ON ORGANOPOLYSILANES;184
7.7.1;SILICON-FUNCTIONAL METHYLPOLYSILANES;184
7.7.2;PERMETHYLATED LINEAR POLYSILANES;188
7.7.3;ALIPHATIC CARBON- FUNCTIONAL ORGANO DI– AND TRISILANES;190
7.7.4;ELEGTROPHILIG AND OXIDATIVE CLEAVAGE OF Si—Si
BONDS;195
7.7.5;ULTRAVIOLET PROPERTIES OF SOME ORGANOPOLYSILANES;201
7.7.6;CONCLUSION;203
7.7.7;References;204
7.8;CHAPTER 13. STRUCTURAL CHEMISTRY OF Si-H COMPOUNDS;206
7.8.1;MOLECULAR GEOMETRY;206
7.8.2;NMR SPECTROSCOPY;211
7.8.3;References;218
7.9;CHAPTER 14. NEUE SPEKTROSKOPISCHE UNTERSUCHUNGEN VON BINDUNGEN IN ORGANOSILICIUMVERBINDUNGEN;220
7.9.1;EINLEITUNG;220
7.9.2;SUBSTITUENTENEINFLUSS AUF CHARAKTERISTISCHE SCHWINGUNGEN;221
7.9.3;LÖSUNGSMITTELEINFLUSS;223
7.9.4;MESSUNGEN AN GYCLOSILOXANEN;225
7.9.5;Literatur;230
7.10;CHAPTER 15. REACTIONS AND REARRANGEMENTS OF CARBON-FUNCTIONAL ORGANOSILICON COMPOUNDS;232
7.10.1;REARRANGEMENTS OF a-SILYLCARBINOLS TO SILYLETHERS;232
7.10.2;THE REARRANGEMENT OF a-SILYLKETONES;241
7.10.3;References;245
7.11;CHAPTER 16. PROBLEMS OF BOND UTILIZATION OF SILICON d-ORBITALS;248
7.11.1;References;262
7.12;CHAPTER 17. POLYMERIC METHYLSILAZANES;264
7.12.1;References;279
7.13;CHAPTER 18. NOVEL WAYS IN THE PREPARATION OF CYCLIC SILICON-NITROGEN COMPOUNDS;280
7.13.1;INTRODUCTION;280
7.13.2;CYCLOSILAZANES AND POLYSILAZANES;280
7.13.3;HALOGENOSILAZANES;282
7.13.4;SILICON-NITROGEN RINGS FROM DIGHLORODISILAZANES;286
7.13.5;RING COMPOUNDS FROM OTHER SILICON-NITROGEN BUILDING UNITS;292
7.13.6;CONCLUSION;294
7.13.7;References;295
7.14;CHAPTER 19. BILDUNG UND EIGENSCHAFTEN VON CARBOSILANEN;298
7.14.1;Literatur;312
7.14.2;CHAPTER 20. THE RADIATION CHEMISTRY OF SILICON COMPOUNDS;314
7.14.3;GENERAL REMARKS ON RADIATION CHEMISTRY;314
7.14.4;SYNTHETIC APPLICATIONS OF RADIATION CHEMISTRY TO SILICON COMPOUNDS;315
7.14.5;MECHANISTIC STUDIES OF THE EFFECTS OF RADIATION ON SILICON COMPOUNDS;322
7.14.6;References;330
7.15;CHAPTER 21. DIRECT SYNTHESIS OF ORGANO-HALOGENOSILANES;332
7.15.1;MECHANISM OF ORGANO-HALOGENOSILANES SYNTHESIS;332
7.15.2;SYNTHESIS OF ALKYLCHLOROSILANES;334
7.15.3;SYNTHESIS OF ARYLHALOGENOSILANES;335
7.15.4;SIDE REACTIONS BY DIRECT SYNTHESIS;337
7.15.5;References;349