Preparation of the complexes trans-[PtX2(CO)L] and their isomerisation to cis isomers

Abstract
Treatment of halide-bridged dimers [{PtX2L}2](X is halide; L is tertiary phosphine or arsine) by carbon monoxide gives solutions of the trans isomers of [PtX2(CO)L], some of which can be isolated. These compounds readily lose CO and isomerise to cis derivatives. The trans to cis isomerisations are catalysed by free CO, phosphines, or halide ions, and the latter nucleophile operates even in the solid phase. Free CO exchanges with co-ordinated CO more rapidly with the trans isomer than the cis. The trans to cis isomerisations are accelerated by light or u.v. irradiation, and u.v. treatment of the thermodynamic cis isomers produces transcis mixtures. The mechanisms of all these processes are discussed.

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