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The chelate phosphanes Diphos, Diop, and Norphos were reacted with C5H5Mn(CO)2THF and CH3C5H4Mn(CO)2THF to give mononuclear complexes, containing the phosphanes as unidentate or as bidentate ligands, and dinuclear complexes, containing bridging phosphane ligands. In C5H5Mn(CO)2Diop one of the two P(C6H5)2 groups of Diop is coordinated to the C5H5Mn(CO)2 fragment; the uncoordinated P(C6H5)2 group makes it a monodentate ligand. C5H5Mn(CO)2Diop together with [Rh(cod)Cl]2 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).