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

Christopher H. Hendon, David R. Carbery, Aron Walsh

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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.
Original languageEnglish
Pages (from-to)1390-1395
Number of pages6
JournalChemical Science
Issue number4
Early online date20 Jan 2014
Publication statusPublished - 1 Apr 2014


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