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AB-initio study of alpha-silyl and beta-silyl substituent effects on vinyl radicals

Lalitha, S and Chandrasekhar, J (1994) AB-initio study of alpha-silyl and beta-silyl substituent effects on vinyl radicals. In: Proceedings of the Indian Academy of Sciences - Chemical Sciences, 106 (2). pp. 259-266.

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The geometries of alpha- and beta-silyl substituted vinyl radicals and of alpha,beta-disilylvinyl radical have been optimised with the STO-3G and the STO-3G* basis sets. The relative stabilities of various conformers have been determined at the UMP2/6-31G* level. The stabilisation of vinyl radicals through alpha-silyl substitution is larger than that due to corresponding alkyl groups. The presence of an alpha-silyl group also leads to a tendency towards linearisation of the vinyl radical centre and a corresponding reduction in the inversion barrier. In marked contrast, the beta-silyl effect is negligible. The geometric, conformational and energetic consequences are insignificant. Overall, the silyl substituent effect at vinyl radicals is very different from that computed earlier for the vinyl cations, but qualitatively similar to that found in carbanions.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to Indian Academy of Sciences.
Department/Centre: Division of Chemical Sciences > Organic Chemistry
Depositing User: Ms V Mangala
Date Deposited: 03 Jun 2011 07:53
Last Modified: 03 Jun 2011 07:53
URI: http://eprints.iisc.ac.in/id/eprint/36094

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