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


Reference:

Hendon, C. H., Carbery, D. R. and Walsh, A., 2014. Three-electron two-centred bonds and the stabilisation of cationic sulfur radicals. Chemical Science, 5 (4), pp. 1390-1395.

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    Official URL:

    http://dx.doi.org/10.1039/c3sc53432d

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    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.

    Details

    Item Type Articles
    CreatorsHendon, C. H., Carbery, D. R. and Walsh, A.
    DOI10.1039/c3sc53432d
    Related URLs
    URLURL Type
    http://www.scopus.com/inward/record.url?scp=84897731895&partnerID=8YFLogxKUNSPECIFIED
    DepartmentsFaculty of Science > Chemistry
    Research CentresCentre for Sustainable Chemical Technologies
    RefereedYes
    StatusPublished
    ID Code39282

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