572914-94-4Relevant academic research and scientific papers
Homo- and Heteronuclear Complexes of (Pentamethylcyclopentadienyl)-rhodium(III) Bearing Bis(diphenylphosphanylmethyl)phenylphosphane
Yamamoto, Yasuhiro,Kosaka, Yosuke,Tsutsumi, Yoshihiro,Kaburagi, Yoshihiro,Kuge, Katsuaki,Sunada, Yusuke,Tatsumi, Kazuyuki
, p. 134 - 142 (2004)
Reaction of [Cp*RhCl2]2 (1) with bis(diphenylphosphanylmethyl)phenylphosphane (dpmp) in the presence of KPF 6 generated the mono- or bi-nuclear complexes [(Cp* RhCl)(dpmp-P,P,P)(RhCl2Cp*)](PF6) (2) or [Cp*RhCl(dpmp-P,P)](PF6) (3), depending on the reaction conditions. These complexes have two chiral centers at Rh and the central P atoms, and the diastereomers were separated by successive recrystallization. The structures of 2(B) with an RRhSp/SRhRP pair and 3(A) with an RRhSp/SRhRp pair were elucidated by X-ray analyses. Reaction of 1 with an excess of dpmp in the presence of Ag(OTf) generated a hetero-tetranuclear complex [{Cp*RhCl 2(dpmp-P,P,P)Ag}2](OTf)2 (4). An X-ray analysis revealed that each Cp*RhCl2 moiety is connected by a terminal P1 atom of the dpmp ligand and each Ag atom is two-coordinate and is surrounded by another terminal P3 atom, and a central P*3 atom of the other dpmp ligand. A mixture of 1 and dpmp was treated with Au(SC4H8) or CuCl in the presence of KPF6, generating the hetero-tetranuclear complexes [{Cp*RhCl2(dpmp-P,P,P)M}2](PF6) 2 (7: M = Au; 8: M = Cu), in which the structures, except for the Cl-bridged structure of 8, are fundamentally similar to that of 4. These complexes were also prepared by the reactions of 3 with Au(SC4H 8) or CuCl. Complex 3 reacted with AgOTf to afford [Cp*Rh(dpmp-P,P,P)](OTf)2 (5). Treatment of 3(A) (a diastereomer with an RRhSP2/SRhRP2 pair) with 1, [(p-cymene)RuCl2]2 or PdCl2(cod) gave [Cp*RhCl(dpmp-P,P,P)RhCl2Cp*](PF6) (2) or [Cp*RhCl(dpmp-P,P,P)RuCl2(p-cymene)](PF6) (6), respectively. These addition reactions proceeded stereoselectively. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
Stereochemistry of mono- and dinuclear complexes of rhodium, iridium and ruthenium bearing bis(diphenylphosphinomethyl)phenylphosphine
Kosaka, Yosuke,Shinozaki, Yuichi,Tsutsumi, Yoshihiro,Kaburagi, Yoshihiro,Yamamoto, Yasuhiro,Sunada, Yusuke,Tatsumi, Kazuyuki
, p. 8 - 12 (2007/10/03)
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 hetero-tetranuclear complex [{Cp*RhCl2(dpmp)Au}2] (PF6)2 (7a), whereas similar reactions of 5c gave dinuclear complex [(C6Me6)RuCl(dpmp)AuCl] (PF6) (8c(A)).
