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.