The University of Southampton
University of Southampton Institutional Repository

Hypervalent interactions in anthraquinone-based Group 15' onium salts - fact or fiction?

Allen, D. W., Coles, S. J., Hursthouse, M. B. and Khan, S. M. (2004) Hypervalent interactions in anthraquinone-based Group 15' onium salts - fact or fiction? Inorganica Chimica Acta, 357, (1), pp. 265-270. (doi:10.1016/S0020-1693(03)00481-X).

Record type: Article


Metal ion-catalysed replacement of bromine in 1-amino-2-methyl-4-bromoanthraquinone by triphenylphosphine and triphenylstibine occurs readily under mild conditions to give the respective phosphonio- and stibonio-anthraquinone salts, the carbonyl group acting as a coordination template for the metal ion, facilitating replacement of the halogen. The extent to which the Group 15 element may be involved in hypercoordination from the adjacent carbonyl oxygen atom in the 'onium salts has been investigated by X-ray crystallography. Both salts involve considerable distortion of bond angles about the Group 15 atom in the direction of trigonal bipyramidal geometry, with phosphorus-oxygen (2.661 Angstrom) and antimony-oxygen (2.497 Angstrom) distances which are well within the sum of the van der Waals radii. In both structures, the Group 15 element and the adjacent carbonyl oxygen atom are bent out of the plane of the anthraquinone system. However, the extent of out of plane deformation is smaller in the case of the larger antimony atom, suggesting that there is a genuine hypercoordinative interaction which increases as the Group is descended.

Full text not available from this repository.

More information

Published date: 9 January 2004
Keywords: crystal structures, catalysis, phosphonium salts, stibonium salts, hypercoordinationo donor action, molecular-structures, phosphorus, coordination, arsonium, bromide, silicon, bearing, crystal, atoms


Local EPrints ID: 20115
ISSN: 0020-1693
PURE UUID: 7a138c9e-a5b0-47f3-8c31-ed00b4e525d6
ORCID for S. J. Coles: ORCID iD

Catalogue record

Date deposited: 23 Feb 2006
Last modified: 17 Jul 2017 16:29

Export record



Author: D. W. Allen
Author: S. J. Coles ORCID iD
Author: S. M. Khan

University divisions

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton:

ePrints Soton supports OAI 2.0 with a base URL of

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.