Homo- and heteronuclear complexes based on arene ruthenium complexes bearing bis(diphenylphosphinomethyl)phenylphosphine (dpmp)

Reactions of (p-cymene)RuCl₂]₂ (1a) with dpmp ((Ph₂PCH₂)₂PPh) in the absence or presence of KPF₆ afforded the ionic complexes {(p-cymene)RuCl₂}(dpmp-P¹,P³;P²){RuCl(p-cymene)}](X) (2a₁: X=Cl; 2a₂: X=PF₆). A (p-cymene)RuCl moiety constructs a 6-membered ring coordinated by two terminal P atoms of the dpmp ligand and another one binds to a central P atom of the ligand. Reactions of (C₆Me₆)RuCl₂]₂ (1b) with an excess of dpmp in the presence of KPF₆ gave a 4-membered complex (C₆Me₆)RuCl(dpmp-P¹,P²)](PF₆) (3b), chelated by a terminal and a central P atom and another terminal atom is free. Use of Ag(OTf) instead of KPF₆ gave {(C₆Me₆)RuCl₂(dpmp)Ag} ₂](OTf)₂ (5b) that the Ag atoms were coordinated by a terminal and a central P atom of each dpmp ligand. Reaction with an equivalent of dpmp in the presence of KPF₆ gave {(C₆Me₆)RuCl}(dpmp-P¹,P²;P³){(C₆Me₆)RuCl₂}](PF₆) 4b. Complex has a structure that the (C₆Me₆)RuCl₂ moiety coordinated to the free P atom of 3b. Complex 3b was treated with MCl₂(cod) (M=Pd, Pt), Pd(MesNC)₄](PF₆)₂ (MesNC=2,4,6-Me₃C₆H₂NC) or Pt₂(XylNC)₆](PF₆)₂ (XylNC=2,6-Me₂C₆H₃NC), generating {(C₆Me₆)RuCl(dpmp)}₂MCl₂](PF₆)₂ (8b: M=Pd; 9b: M=Pt), {(C₆Me₆)RuCl(dpmp)}₂{Pt(MesNC)₂}](PF₆)₄ (10b) and {(C₆Me₆)RuCl(dpmp)}₂{Pt₂(XylNC)₄}](PF₆)₄ (11b), respectively. Complex 3b reacted readily with Cp*MCl₂]₂ (M=Rh, Ir) or AuCl(SC₄H₈), affording the corresponding hetero-binuclear complexes {(C₆Me₆)RuCl}(dpmp-P¹,P²;P³)(MCl₂Cp^*](PF₆) (6b: M=Rh; 7b: M=Ir) and {(C₆Me₆)RuCl}(dpmp-P¹,P²;P³)(AuCl)](PF₆) (12b). These complexes have two chiral centers. Some complexes were separated as two diastereomers by successive recrystallization. The structures of 3b, 5b, 6b, 8b and 12b were confirmed by X-ray analyses.