Asymmetrische Katalysen, 25 [1]. C₅H₅Mn(CO)₂-Komplexe von optisch aktiven Chelatphosphanen als einzähnige Liganden in der enantioselektiven Katalyse / Asymmetric Catalyses, 25 [1]. C₅H₅Mn(CO)₂ Complexes of Optically Active Chelate Phosphanes as Monodentate Ligands in Enantioselective Catalysis

Abstract

<jats:p>The chelate phosphanes Diphos, Diop, and Norphos were reacted with C<jats:sub>5</jats:sub>H<jats:sub>5</jats:sub>Mn(CO)<jats:sub>2</jats:sub>THF and CH<jats:sub>3</jats:sub>C<jats:sub>5</jats:sub>H<jats:sub>4</jats:sub>Mn(CO)<jats:sub>2</jats:sub>THF to give mononuclear complexes, containing the phosphanes as unidentate or as bidentate ligands, and dinuclear complexes, containing bridging phosphane ligands. In C<jats:sub>5</jats:sub>H<jats:sub>5</jats:sub>Mn(CO)<jats:sub>2</jats:sub>Diop one of the two P(C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub>)<jats:sub>2</jats:sub> groups of Diop is coordinated to the C<jats:sub>5</jats:sub>H<jats:sub>5</jats:sub>Mn(CO)<jats:sub>2</jats:sub> fragment; the uncoordinated P(C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub>)<jats:sub>2</jats:sub> group makes it a monodentate ligand. C<jats:sub>5</jats:sub>H<jats:sub>5</jats:sub>Mn(CO)<jats:sub>2</jats:sub>Diop together with [Rh(cod)Cl]<jats:sub>2</jats:sub> was used as an in situ catalyst in the enantioselective hydrogenation of (Z)-a-[N -acetam ino]cinnamic acid (78.4% ee) and in the enantioselective hydrosilylation of acetophenone with diphenylsilane (6.7% ee).</jats:p>