Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanes

Abstract

Enantiopure P-stereogenic methylphosphane-boranes (S_P)-P(BH₃)PhArMe (ArMe; Ar = 1-naphthyl (NpMe), and 2-biphenylyl (BiphMe)) have been used to prepare diphosphanes of the type ArPhPCH₂PR₂ (R = Ph, iPr or tBu; ArR). The ligands have been reacted with [Rh(COD)₂]BF₄ to furnish the corresponding six monochelated [Rh(COD)(ArR)]BF₄ organometallic compounds (RhArR) or, depending on the reaction conditions, the bis(chelated) coordination compound [Rh(BiphiPr)₂]BF₄ as a mixture of cis and trans isomers. The crystal structure of cis-[Rh(BiphiPr)₂]BF₄ was obtained. The coordination of the BiphR with [RuCl(μ-Cl)(η⁶-p-cymene)₂]₂ under different conditions produced cationic chelated complexes of the type [RuCl(η⁶-p-cymene)(κ²-BiphR)]PF₆ (RuBiphR) and the neutral monocoordinated complex [RuCl₂(η⁶-p-cymene)(κ¹-BiphPh)] (RuBiphPh′) with the uncoordinated P-stereogenic moiety. The Rh(I) complexes were used in the catalytic hydrogenation of functionalized olefins and the Ru(II) complexes were tested in the transfer hydrogenation of acetophenone. Both precursors displayed good activities with moderate enantioselectivities.