Using the unsymmetrical P–P′ phospholyl(phosphino)methane ligand, complex cis-[RuCl2(κ2-P–P′)2] is easily prepared from [RuCl2(DMSO)4]. The two phosphole-phosphorus atoms lie in the trans position to the two cis-chloro ligands. This complex slowly isomerizes spontaneously at 20 °C to the trans-[RuCl2(κ2-P–P′)2] diastereoisomer where the two phosphole moieties are mutually trans, as well as the two chloro ligands and the two Ph2P moieties. DFT calculations show that this non-classical cis–trans isomerisation process requires a 3 kcal mol−1 energy and involves the decoordination of a phosphole arm.
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