Novel phospholyl(diphenylphosphino)methane-ruthenium complexes: Unexpected non-assisted cis to trans isomerization of [RuCl2(κ 2-P-P′)2]

Article abstract of DOI:10.1039/c2dt32032k

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. The Royal Society of Chemistry 2013.