Issue 4, 2014

Three-electron two-centred bonds and the stabilisation of cationic sulfur radicals

Abstract

Electronic communication in biological systems is fundamental to understanding protein signalling and electron hopping pathways. Frequently studied examples are cationic radical methionine and its functional derivatives. These systems are understood to be stabilised by a direct ‘three-electron two-centred’ bond. We demonstrate for methionine and a series of cationic radical methionine analogues that long-range multi-centred indirect stabilisation occurs, which cannot be attributed to three-electron two-centred interactions. A revised description of the radical stabilisation process is presented, which includes contributions from all atoms with accessible p-orbitals, independent of the distance to the sulfur radical.

Graphical abstract: Three-electron two-centred bonds and the stabilisation of cationic sulfur radicals

Article information

Article type
Edge Article
Submitted
14 Dec 2013
Accepted
20 Jan 2014
First published
20 Jan 2014
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2014,5, 1390-1395

Author version available

Three-electron two-centred bonds and the stabilisation of cationic sulfur radicals

C. H. Hendon, D. R. Carbery and A. Walsh, Chem. Sci., 2014, 5, 1390 DOI: 10.1039/C3SC53432D

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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