Stereochemistry of mono- and dinuclear complexes of rhodium, iridium and ruthenium bearing bis(diphenylphosphinomethyl)phenylphosphine

Reaction of [Cp*MCl 2 ] 2 ( 1a : M=Rh and 1b : M=Ir) or [(C 6 Me 6 )RuCl 2 ] 2 ( 1c ) with bis(diphenylphosphinomethyl)phenylphosphine (dpmp) in the presence of KPF 6 generated mono- or dinuclear complexes [Cp*RhCl(dpmp)](PF 6 ) ( 2a ), [(C 6 Me 6 )RuCl(dpmp)](PF 6 ) ( 5c ), [Cp*MCl 2 (dpmp)MClCp*](PF 6 ) ( 3a : M=Rh and 4b : M=Ir) or [(C 6 Me 6 )RuCl 2 (dpmp)RuCl(C 6 Me 6 )](PF 6 ) ( 6c ), depending on reaction conditions. These complexes have two chiral centers and the diastereomers were separated and characterized by spectrometry and X-ray analyses. A diastereomer 2a ( A ) was treated with AuCl(C 4 H 8 S), generating a hetero-tetranuclear complex [{Cp*RhCl 2 (dpmp)Au} 2 ](PF 6 ) 2 ( 7a ), whereas similar reactions of 5c gave dinuclear complex [(C 6 Me 6 )RuCl(dpmp)AuCl](PF 6 ) ( 8c ( A )).