Synthesis and structure of some binuclear carbonyl complexes of platinum(I)

Abstract
The complex [Pt2Cl2(µ-CO)(µ-dppm)2][2; dppm = bis(diphenylphosphino)methane] has been prepared by the reversible reaction of [Pt2Cl2(µ-dppm)2] with carbon monoxide and also by the reaction of [NPr4]2[Pt2Cl4(CO)2] with dppm. In polar solvents (2) isomerises to give the ion [Pt2Cl(CO)(µ-dppm)2]+, isolated as the [PF6] salt (3b). The i.r., Raman, and 1H and 31P n.m.r. spectra of these complexes are discussed. On the basis of its exceptionally low i.r. frequency, it is proposed that the carbonyl group in complex (2) is acting as an unsymmetrical four-electron bridging ligand. An arsine complex [Pt2Cl2(µ-CO)(µ-dpam)2][dpam = bis(diphenylarsino) methane] analogous to (2) has been prepared from [Pt2Cl4(CO)2]2–.

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