572915-02-7Relevant articles and documents
Homo- and heteronuclear complexes based on arene ruthenium complexes bearing bis(diphenylphosphinomethyl)phenylphosphine (dpmp)
Yamamoto, Yasuhiro,Sinozuka, Yuichi,Tsutsumi, Yoshihiro,Fuse, Kei,Kuge, Katsuaki,Sunada, Yusuke,Tatsumi, Kazuyuki
, p. 1270 - 1282 (2008/10/09)
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.
