Abstract
Abstract(R)‐methylbinapium, a Hayashi‐type phosphonium‐MOP ligand, reacts with [Rh(cod)2][BF4] in ethanol to afford the chiral mixed bis(monophosphane)rhodium(I) complex [Rh(η5‐H‐MOP)(MePh2P)][BF4]. The constitutional and geometrical features of this complex have been determined by exhaustive 1H, 11B, 13C, 31P and 103Rh 1‐D, 2‐D and NOE NMR spectroscopy and optical rotation measurements. The chelating η5‐(γ‐phosphanyldiene) ligand character of H‐MOP in this complex is an extension to RhI of similar coordination modes studied by Pregosin in the coordination sphere of RuII. The process of its formation relies on an enantiospecific reductive cleavage of a P+−C bond, which is also reminiscent of Pregosin’s P−C bond cleavages in the ruthenium series. The complex is a catalytic precursor for the hydrogenation of (Z)‐α‐acetamidocinnamic acid. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
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