# Towards stable distonic radical anions: A theoretical study

Pius, Kuruvilla and Chandrasekhar, Jayaraman (1988) Towards stable distonic radical anions: A theoretical study. In: Journal of the Chemical Society, Perkin Transactions II (7). pp. 1291-1295.

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## Abstract

Ab initio molecular orbital calculations have been carried out to obtain the structures and relative isomer energies of organometallic radical anions of the types $CH_3X^{-\cdot}$ and $H_2C^{\cdot}-XH^-$ $(X = Li, BeH, BH_2, Na, MgH, or AIH_2)$. Comparison with results for the corresponding neutral molecules indicates a dramatic reduction in the energy gap between classical and hydrogen-shifted isomers on addition of an electron. However, the classical isomers of the radical anions generally represent the preferred form. The only exception is $H_2C^{\cdot}-BH_3^ {-}$, which is calculated to be virtually isoenergetic with $H_3CBH_2 ^{-\cdot}$. Organoborane radical anions are thus the most likely systems to adopt distonic structures with the formal charge and radical centres on different atoms. Further separation of the charge and the radical sites through homologation is predicted to be ineffective in stabilising the distonic structures. MNDO calculations on larger models point to experimentally accessible distonic radical anions. The present study leads to a better understanding of the origin of distonic stabilisation in radical ions.

Item Type: Journal Article Copyright of this article belongs to Royal Society of Chemistry. Division of Chemical Sciences > Organic Chemistry 29 Feb 2008 19 Sep 2010 04:42 http://eprints.iisc.ernet.in/id/eprint/13126