Redox-controlled interconversion between trigonal prismatic and octahedral geometries in a monodithiolene tetracarbonyl complex of tungsten

Yan, Y., Chandrasekaran, P., Mague, J. T., DeBeer, S., Sproules, S. and Donahue, J. P. (2012) Redox-controlled interconversion between trigonal prismatic and octahedral geometries in a monodithiolene tetracarbonyl complex of tungsten. Inorganic Chemistry, 51(1), pp. 346-361. (doi:10.1021/ic201748v)

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Abstract

The monodithiolene compound [W(S2C2Me2)(CO)4], 1, is an unusual example of a trigonal prismatic compound with multiple π-acid ligands. This geometry arises in part from a HOMO−LUMO configuration interaction (both b1), which is lost if the geometry is changed to octahedral. One-electron reduction of 1, which induces a change to octahedral geometry, involves two-electron reduction of tungsten and one-electron oxidation of dithiolene ligand. The properties of 1 (W(ll), d4) are contrasted with those of [W(Me2pipdt)(CO)4], (W(0), d6).

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Sproules, Dr Stephen
Authors: Yan, Y., Chandrasekaran, P., Mague, J. T., DeBeer, S., Sproules, S., and Donahue, J. P.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Inorganic Chemistry
Publisher:American Chemical Society
ISSN:0020-1669
ISSN (Online):1520-510X

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