Many organometallic enzymes that are responsible for redox reactions contain dithiolene ligands. To better understand the importance of the dithio ligands, we have synthesized novel dithiolate transition metal compounds. The dithiolate-bridged compound [CpMo(�-S2C2H4)]2 loses its ethylene bridges on heating, providing reactive sites at its bridging sulfur atoms. We have reacted this molybdenum dimer with group 6-8 transition metal carbonyl complexes to effect replacement of one or both ethylene bridges with transition metal carbonyl fragments. Depending on the transition metal, the metal carbonyl fragments may bridge the sulfurs symmetrically or asymmetrically; one product, [(CpMo)2{Os(CO)2}2(�3-S)4], adopts a cubane structure. These new complexes have been characterized and identified by X-ray crystallography, NMR and IR spectroscopy and APCI mass spectrometry.

Synthesis of sulfur-bridged transition metal organometallic compounds by ethylene bridge replacement

243rd National Meeting (2012)

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