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 heterotetranuclear complex [{Cp*RhCl2(dpmp)Au}(2)](PF6)(2) (7a), whereas similar reactions of 5c gave dinuclear complex [(C6Me6)RuCl(dpmp)AuCl](PF6) (8c(A)). (C) 2003 Elsevier Science B.V. All rights reserved.