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

Reaction of [Cp*MCl2]2 (1a: M=Rh and 1b: M=Ir) or [(C6Me6)RuCl2]2 (1c) with bis(diphenylphosphinomethyl)phenylphosphine (dpmp) in the presence of KPF6 generated mono- or dinuclear complexes [Cp*RhCl(dpmp)](PF6) (2a), [(C6Me6)RuCl(dpmp)](PF6) (5c), [Cp*MCl2(dpmp)MClCp*](PF6) (3a: M=Rh and 4b: M=Ir) or [(C6Me6)RuCl2(dpmp)RuCl(C6Me6)](PF6) (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(C4H8S), generating a hetero-tetranuclear complex [{Cp*RhCl2(dpmp)Au}2](PF6)2 (7a), whereas similar reactions of 5c gave dinuclear complex [(C6Me6)RuCl(dpmp)AuCl](PF6) (8c(A)).