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

Article abstract of DOI:10.1016/j.ica.2003.10.018

Reactions of [(p-cymene)RuCl₂]₂ (1a) with dpmp ((Ph₂PCH₂)₂PPh) in the absence or presence of KPF₆ afforded the ionic complexes [{(p-cymene)RuCl ₂}(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-P ¹, 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 [{(C₆Me ₆)RuCl}(dpmp-P¹, P²; P³){(C ₆Me₆)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 MCl ₂(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 [{(C ₆Me₆)RuCl(dpmp)}₂MCl₂](PF ₆)₂ (8b: M = Pd; 9b: M = Pt), [{(C₆Me ₆)RuCl(dpmp)}₂{Pt(MesNC)₂}](PF ₆)₄ (10b) and [{(C₆Me₆)RuCl(dpmp)} ₂{Pt₂(XylNC)₄}](PF₆)₄ (11b), respectively. Complex 3b reacted readily with [Cp*MCl ₂]₂ (M = Rh, Ir) or AuCl(SC₄H₈), affording the corresponding hetero-binuclear complexes [{(C₆Me ₆)RuCl}(dpmp-P¹, P²; P³)(MCl ₂Cp*](PF₆) (6b: M = Rh; 7b: M = Ir) and [{(C ₆Me₆)RuCl}(dpmp-P¹, P²; P ³)(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.