Chemistry of Oxidometal (Mo and V) Complexes: Metal Assisted Organic Transformation and Novel Solution Behavior

Abstract

The chemistry of oxidomolybdenum and oxidovanadium complexes has gained substantial research importance in recent times due to their versatile reactivity and interesting coordination behaviour. Among them, metal-metal bonded molybdenum(V) complexes constitute an important class of compounds. Very few bis-μ-imido bridged metal-metal bonded oxidomolybdenum(V) complexes are reported in literature, although molybdenum(V) complexes with terminal imide groups have been long known. Further, metal assisted organic transformations of ligands have gained renewed interests in recent years. On another hand, in comparison to the well-known oxidovanadium(IV)/(V) complexes, relatively few non-oxido VIV complexes, have been isolated and structurally characterized. Interestingly, the solid state chemistry for a particular compound may be different from that in solution. Also mixed-valence metal complexes have received much attention. Hence, we have been motivated to focus on our present work1-6 which comprises of the chemistry of variable valence oxidometal (Mo and V) complexes. Mechanistic pathways of metal assisted ligand rearrangements have been predicted. Some bis-μ-imido bridged dimeric oxidomolybdenum(V) complexes synthesised from salophen has been reported. A novel μ-oxidodivanadium compound, generated from the corresponding mononuclear complex, was characterized in solution and in the solid state. The mixed oxidation V(IV,V) species were detected through electro synthesis and characterized by EPR spectroscopy and DFT calculations.