Five-coordinate Pd(II) orthometallated triarylphosphite complexes

Bedford, R. B., Betham, M., Butts, C. P., Coles, S. J., Cutajar, M., Gelbrich, T., Hursthouse, M. B., Scully, P. N. and Wimperis, S. (2007) Five-coordinate Pd(II) orthometallated triarylphosphite complexes. Dalton Transactions, 4, pp. 459-466. (doi: 10.1039/b613524b)

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Publisher's URL: http://dx.doi.org/10.1039/b613524b

Abstract

The reaction of the orthopalladated triarylphosphite complexes [{Pd(μ-Cl){κ2-P,C-P(OC6H2-2,4-R2)(OC6H3-2,4-R2)}2] (R = H, tBu) with bis(2-diphenylphosphinoethyl)phenylphosphine leads to a five-coordinate palladium(II) (R = H) and a mixture containing four-and five-coordinate species (R = tBu). The crystal structure of the five-coordinate species [Pd{κ2-P,C-(P(OC6H4)(OC6H5)2}{bis(2-diphenylphosphinoethyl)phenylphosphine}][SbF6] is presented. This complex reacts with hydrogen peroxide or [AuCl(tht)] to give four-coordinate complexes in which the displaced phosphine residue is either oxidised or coordinated to gold chloride; this demonstrates that the five-coordinate complexes are labile in solution. By contrast, the reactions of the dimeric precursors with 1,1,1-tris(diphenylphosphinomethyl)ethane give four-coordinate complexes in the solid state, although evidence is presented that the smaller phosphite-containing system is five-coordinate at room temperature or higher in solution.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Wimperis, Professor Stephen
Authors: Bedford, R. B., Betham, M., Butts, C. P., Coles, S. J., Cutajar, M., Gelbrich, T., Hursthouse, M. B., Scully, P. N., and Wimperis, S.
Subjects:Q Science > QD Chemistry
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Dalton Transactions
Publisher:Royal Society of Chemistry
ISSN:1477-9226
ISSN (Online):1477-9234
Published Online:12 December 2006

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