Ab initio study of α- and α- silyl substituent effects on vinyl radicals

Lalitha, S. ; Chandrasekhar, Jayaraman (1994) Ab initio study of α- and α- silyl substituent effects on vinyl radicals Proceedings of the Indian Academy of Sciences - Chemical Sciences, 106 (2). pp. 259-266. ISSN 0253-4134

[img]
Preview
PDF - Publisher Version
1MB

Official URL: http://www.ias.ac.in/j_archive/chemsci/106/5/259-2...

Related URL: http://dx.doi.org/10.1007/BF02840748

Abstract

The geometries of α-and β-silyl substituted vinyl radicals and of α, β-disilylvinyl radical have been optimised with the STO-3G and the STO-3G basis sets. The relative stabilities of various conformera have been determined at the UMP2/6-31G level. The stabilisation of vinyl radicals through α-silyl substitution is larger than that due to corresponding alkyl groups. The presence of an α-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 β-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:Article
Source:Copyright of this article belongs to Indian Academy of Sciences.
Keywords:Ab Initio; MO Calculations; Silyl Substituent Effect; Vinyl Radical
ID Code:7535
Deposited On:25 Oct 2010 11:13
Last Modified:16 May 2016 17:42

Repository Staff Only: item control page