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Synthesis and Chemistry of Selected Di- and Tricoordinate Organosilicon Compounds William F

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Synthesis and Chemistry of Selected Di- and Tricoordinate Organosilicon Compounds William F Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1982 Synthesis and chemistry of selected di- and tricoordinate organosilicon compounds William F. Goure Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Goure, William F., "Synthesis and chemistry of selected di- and tricoordinate organosilicon compounds " (1982). Retrospective Theses and Dissertations. 8344. https://lib.dr.iastate.edu/rtd/8344 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. INFORMATION TO USERS This reproduction was made from a copy of a document sent to us for microfilming. While the most advanced technology has been used to photograph and reproduce this document, the quality of the reproduction is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help clarify markings or notations which may appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure complete continuity. 2. Wiien an image on the film is obliterated with a round black mark, it is an indication of either blurred copy because of movement during exposure, duplicate copy, or copyrighted materials that should not have been filmed. For blurred pages, a good image of the page can be found in the adjacent frame. If copyrighted materials were deleted, a target note will appear listing the pages in the adjacent frame. 3. When a map, drawing or chart, etc., is part of the material being photographed, a definite method of "sectioning" the material has been followed. It is customary to begin filming at the upper left hand comer of a large sheet and to continue from left to right in equal sections with small overlaps. If necessary, sectioning is continued again—beginning below the first row and continuing on until complete. 4. For illustrations that cannot be satisfactorily reproduced by xerographic means, photographic prints can be purchased at additional cost and inserted into your xerographic copy. These prints are available upon request from the Dissertations Customer Services Department. 5. Some pages in any document may have indistinct print. In all cases the best available copy has been filmed. Uni International 300 N. Zeeb Road Ann Arbor, Ml 48106 8307747 Goure, William F. SYNTHESIS AND CHEMISTRY OF SELECTED DI- AND TRICOORDINATE ORGANOSILICON COMPOUNDS Iowa State University PH.D. 1982 University Microfilms Intsrnatlonsl 300 N. Zeeb Road. Ann Arbor. MI 48106 Synthesis and chemistry of selected di- and tricoordinate organosilicon compounds by William F. Goure A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Department: Chemistry Major: Organic Chemistry Approved: Signature was redacted for privacy. Charge of Ma^or Work Signature was redacted for privacy. A)r the ftejor Department Signature was redacted for privacy. For the Sr^du^e College Iowa State University Ames, Iowa 1982 ii TABLE OF CONTENTS Page INTRODUCTION 1 NOMENCLATURE 3 HISTORICAL 5 Silylenes 5 Silyl Radicals 75 RESULTS AND DISCUSSION 136 Attempted Preparation of Silaoxetanes Utilizing Silylene Insertion Reactions 136 The addition of Dimethylsilylene to Cyclooctatetraene (COT) 161 Intramolecular Reactions of Silylenes 157 Investigation of the Thermal- and Photochemistry of 7-Silanorbornadienes 212 The Preparation and Chemistry of Alkenyl-Substituted Silyl Radicals 235 The Reaction of Diallyldimethylsilane with Trichloromethyl Radical 269 CONCLUSIONS 277 Suggestions for Future Work 278a EXPERIMENTAL 279 General Information 279 Procedures and Results 280 BIBLIOGRAPHY 387 ACKNOWLEDGEMENTS 404 1 INTRODUCTION Although the chemistry of silylenes - silicon analogues of carbenes - began over forty years ago with the discovery of dichlorosilylene (1,2), our current understanding of these interesting molecules is based primarily on the results of studies conducted within the last two decades. Indeed, the development of organosilylene chemistry did not begin until the early 1960s when Skell and Goldstein reported the generation of the first organo­ silylene (3). Even then, it was not until the pioneering work of Gilman and coworkers (4,5) and Atwell and Weyenberg (6,7) that the development of silylene chemistry began in earnest. Throughout the last twenty years, silylene chemistry has been extensively investigated, and continues today unabated. In some aspects, the chemistry of silyl radicals is similar to that of silylenes. Thus, less than fifty years ago the first silyl radicals were discovered. Although interest in the chemistry of silyl radicals has paralleled that of silylenes. the lack of convenient methods for the clean production of silicon based radicals has retarded advancements in this field of silicon chemistry. Despite this shortcoming, the last two decades have witnessed a substantial increase in our understanding of silyl radicals. This thesis will present the results of four primary investigations: a) the attempted utilization of silylenes as synthons for silaoxetanes; b) the preparation and chemistry of selected silylenes which contained substituants and were generated under conditions such that intramolecular rearrangements would be favored; c) the thermal- and photochemistry of 7- 2 silanorbornadienes; and d) the preparation and chemistry of alkenyl- substituted silyl radicals. In addition to these main areas of investiga­ tion, the results obtained from a study of the addition of dimethyl silylene to cyclooctatetraene and a brief study of the addition of Cl^C- to diallyldimethylsilane will be described. 3 NOMENCLATURE The nomenclature used in this thesis will, with the exceptions described below, follow the conventions set down by lUPAC. Simple organosilicon compounds will be named as derivatives of silane (SiH^) while more complicated linear and cyclic systems will be named as sila- analogs of the corresponding carbon systems. Divalent silicon species will be named as derivatives of the parent silylene (iSiHg). Examples : MegSiClH dimethylchlorosi1ane CI t Me^Si-Si-CH=CH2 1-chl oro-l-vinyltetramethyldi si1ane Me H I 2-methyl-2-sila-o-heptene Me Me \ / Si 1,1,4,4-tetramethyl-l ,4-disilin Si /\ Me Me 4 Silicon centered radicals will be named as derivatives of the parent silyl radical (HL,Si"). Examples : Me^Si- trimethylsilyl radical Me Me^SiSi" (trimethylsilyl)dimethylsilyl Me radical Me PhCHgCHgCHgSi' (3-phenylpropyl)dimethylsilyl Me radical Three membered rings containing a silicon and two carbon atoms will be named as derivatives of silarane or silacyclopropane and silarene or silacyclopropene. Silacyclopentadienes will be named as derivatives of silole. Examples : Me Me \ / y I 1,1-dimethylsilarane or 1,1-dimethylsilacyclopropane 5 Me Me \/ 1 J-dimethylsilarene or 1,1-dimethyl silacyclopropene Me Me \/ 1,1-dimethyl-2,5-di phenylsilole Finally, the [2,2,1] bicycloheptene and heptadiene ring systems, containing a silicon at the seven position, will be named as derivatives of 7-silanorbornene and 7-silanorbornadiene. Examples : ne ne \ / Si Ph 1 j4._dT phenyl-2,3-dicarbomethoxy- Ph^^COgMe 7,7-dimethyl-7-silanorborna-5-ene Me Me Si Ph COgMe 1,4-diphenyl-2,3-dicarbomethoxy- 7,7-dimethyl-7-si1anorbornadi ene COgMe 5 HISTORICAL Silylenes have been extensively reviewed (8-14). Thus, to prevent duplication, a complete survey of the chemistry of silylenes will not be presented. Instead, the review of the known chemistry of silylenes will concentrate on those aspects, particularly the advances made within the last two decades, that have contributed the most to our understanding of silylenes. The chemistry of difluorosilylene, which in many ways is differ­ ent from the chemistry of all other silylenes, will not be presented since it has been adequately reviewed elsewhere (8-14). Silyl radicals have also been the subject of several reviews (15-18). However, a number of significant advances have occurred in this field of silicon chemistry since the last review; thus, a more extensive survey of the known chemistry of silyl radicals will be presented. Silylenes The preparation and spectral observation of the first silylene, dichlorosilylene, was reported over 40 years ago (1,2). Although this discovery was contemporary to the beginnings of carbene chemistry, the development of silylene chemistry has lagged behind that of carbenes. This was due in part to a dearth of convenient methods of silylene generation prior to 1962. Indeed, the existence of the first organosilylene, dimethyl- silylene, was confirmed less than two decades ago. The electronic configuration and molecular geometry of inorganic silylenes, the dihydrides and mono- and dihalides, have been the subject of numerous studies, both theoretical and experimental, Nefedov has conven­ 7 iently tabulated these data (11). The mono- and dihalides are known to have a singlet ground
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