Unprecedented stereoselective synthesis of catalytically active chiral Mo3CuS4 clusters

Cluster excision of polymeric {Mo3S7Cl4}n phases with chiral phosphane (+)-1,2-bis(2R,5R)-2,5-(dimethylphospholan-1-yl)]ethane ((R,R)-Me-BPE) or with its enantiomer ((S,S)-Me-BPE) yields the stereoselective formation of the trinuclear cluster complexes Mo3S4{(R,R)-Me-BPE}3Cl3]+ ((P)-1]+) and Mo3S4{(S,S)-Me-BPE}3Cl3]+ ((M)-1]+), respectively. These complexes possess an incomplete cuboidal structure with the metal atoms defining an equilateral triangle and one capping and three bridging sulfur atoms. The P and M symbols refer to the rotation of the chlorine atoms around the C3 axis, with the capping sulphur atom pointing towards the viewer. Incorporation of copper into these trinuclear complexes affords heterodimetallic cubane-type compounds of formula Mo3CuS4{(R,R)-Me-BPE}3Cl4]+ ((P)-2]+) or Mo3CuS4{(S,S)-Me-BPE}3Cl4]+ ((M)-2]+), respectively, for which the chirality of the trinuclear precursor is preserved in the final product. Cationic complexes (P)-1]+, (M)-1]+, (P)-2]+, and (M)-2]+ combine the chirality of the metal cluster framework with that of the optically active diphosphane ligands. The known racemic Mo3CuS4(dmpe)3Cl4]+ cluster (dmpe = 1,2-bis(dimethylphosphanyl)ethane) as well as the new enantiomerically pure Mo3CuS4 (P)-2]+ and (M)-2]+ complexes are efficient catalysts for the intramolecular cyclopropanation of 1-diazo-5-hexen-2-one (3) and for the intermolecular cyclopropanation of alkenes, such as styrene and 2-phenylpropene, with ethyl diazoacetate. In all cases, the cyclopropanation products were obtained in high yields. The diastereoselectivity in the intermolecular cyclopropanation of the alkenes and the enantioselectivity in the inter- or intramolecular processes are only moderate.