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• 572914-94-4 [(bis(diphenylphosphanylmethyl)phenylphosphane-P,P)(pentamethylcyclopentadienyl)chlororhodium(III)] hexafluorophosphate 

Relevant academic research and scientific papers

Homo- and Heteronuclear Complexes of (Pentamethylcyclopentadienyl)-rhodium(III) Bearing Bis(diphenylphosphanylmethyl)phenylphosphane

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.