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http://hdl.handle.net/11375/8398
Title: | Study of 1-metalated-2-(trimethylsilyl)vinyl cations: An examination of the β-effect for silyl, germyl and stannyl groups |
Authors: | Dallaire, Carol |
Advisor: | Brook, Michael A. |
Department: | Chemistry |
Keywords: | Chemistry;Chemistry |
Publication Date: | Sep-1991 |
Abstract: | <p>The ability of silicon, germanium and tin elements (group 14) to stabilize a vinyl cation intermediate was investigated upon proton addition to metalated (trimethylsilyl)acetylene compounds to lead, after demetalation, to monometalated acetylenes. The reactions were followed by ¹H NMR spectroscopy. A bimolecular addition mechanism is obtained and nucleophilic participation in the reaction is observed. The reaction rates showed that vinyl cations are stabilized by hyperconjugation of the carbon-metal bond (β-effect) in the order of magnitude Sn (10⁸) > Ge (500) > Si (1). The magnitude of the β-effect on vinyl cation is altered to a degree by the groups born by the metal. The vinyl cations are stabilized, in a lower extent, by inductive effects of the metalated group to the electron-deficient carbon (α-effect).</p> |
URI: | http://hdl.handle.net/11375/8398 |
Identifier: | opendissertations/3605 4622 1669047 |
Appears in Collections: | Open Access Dissertations and Theses |
Files in This Item:
File | Size | Format | |
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fulltext.pdf | 2.9 MB | Adobe PDF | View/Open |
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