Ancillary ligand effects upon dithiolene ligand noninnocence in tungsten bis(dithiolene) compounds

Yan, Y., Keating, C., Chandrasekaran, P., Jayarathne, U., Mague, J. T., DeBeer, S., Lancaster, K. M., Sproules, S. , Rubtsov, I. V. and Donahue, J. P. (2013) Ancillary ligand effects upon dithiolene ligand noninnocence in tungsten bis(dithiolene) compounds. Inorganic Chemistry, 52(11), pp. 6743-6751. (doi:10.1021/ic4009174)

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Abstract

An expanded set of compounds of the type [W(S2C2Me2)2L1L2]n (n = 0: L1 = L2 = CO, 1; L1 = L2 = CNtBu, 2; L1 = CO, L2 = carbene, 3; L1 = CO, L2 = phosphine, 4; L1 = L2 = phosphine, 5. n = 2−: L1 = L2 = CN−, [6]2−) has been synthesized and characterized. Despite isoelectronic formulations, the compound set reveals gradations in dithiolene ligand redox level as revealed by intraligand bond lengths, υCCchelate, and rising edge energies in the sulfur K-edge X-ray absorption spectra (XAS). Differences between the terminal series members, 1 and [6]2−, are comparable to differences seen in homoleptic dithiolene complexes related by full electron transfer to/from a dithiolene-based MO.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Sproules, Dr Stephen
Authors: Yan, Y., Keating, C., Chandrasekaran, P., Jayarathne, U., Mague, J. T., DeBeer, S., Lancaster, K. M., Sproules, S., Rubtsov, I. V., 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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