Synthesis of thiometallate complexes and catalytic hydration of acetonitrile

The bimetallic complexes [M(bipy)nS2M′X2], where M=FeII, RuII, NiII or CoII; bipy=2,2′-bipyridine; n=1 or 2; M′=MoVI or WVI and X=O or S, were synthesized using tetrathiometallates and dithiometallates as bidentate ligands. The characterization of the new bimetallic complexes was carried out by standard techniques. The complexes were tested as catalysts in acetonitrile hydrolysis. The reaction products are acetamide and acetic acid, formed by hydrolysis of acetamide. The most active catalysts in the acetonitrile hydrolysis are [Fe(bipy)2S2MoS2], [Ru(bipy)2S2MoS2] and [Co(bipy)2S2WS2], whereas the lowest activity is shown by the nickel complexes. However, the latter exhibit the highest selectivity in acetamide formation. ZINDO semi-empirical calculations were performed in order to explain some of the properties of the complexes. This revised version was published online in June 2006 with corrections to the Cover Date.