Five-coordinate Pd(II) orthometallated triarylphosphite complexes

Bedford, Robin B., Betham, Michael, Butts, Craig P., Coles, Simon J., Cutajar, Marica, Gelbrich, Thomas, Hursthouse, Michael B., Scully, P. Noelle and Wimperis, Stephen (2007) Five-coordinate Pd(II) orthometallated triarylphosphite complexes. Dalton Transactions, (4), 459-466. (doi:10.1039/b613524b).

Abstract

The reaction of the orthopalladated triarylphosphite complexes[{Pd(mu-Cl){kappa(2)-P,C-P(OC6H2-2,4- R-2)-(OC6H(3)-2,4-R-2)}(2)] (R = H, Bu-t) with bis(2-diphenylphosphinoethyl)phenylphosphine leads to a five-coordinate palladium(II) (R = H) and a mixture containing four- and five-coordinate species (R = Bu-t). The crystal structure of the five-coordinate species [Pd{kappa(2)-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.

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Contributors

Author: Simon J. Coles

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