A Comparative Study of Molybdenum Carbonyl and Oxomolybdenum Derivatives Bearing 1,2,3-Triazole or 1,2,4-Triazoles in Catalytic Olefin Epoxidation.

The molybdenum(0)-carbonyl-triazole complexes [Mo(CO)₃(L)₃] [L = 1,2,3-triazole (1,2,3-trz) or 1,2,4-triazole (1,2,4-trz)] have been prepared and examined as precursors to molybdenum(VI) oxide catalysts for the epoxidation of cis-cyclooctene. Reaction of the carbonyl complexes with the oxidant tert-butyl hydroperoxide (TBHP) (either separately or in situ) gives oxomolybdenum(VI) hybrid materials that are proposed to possess one-dimensional polymeric structures in which adjacent oxo-bridged dioxomolybdenum(VI) moieties are further linked by bidentate bridging triazole (trz) ligands. A pronounced ligand influence on catalytic performance was found and the best result (quantitative epoxide yield within 1 h at 70 °C) was obtained with the 1,2,3-triazole oxomolybdenum(VI) hybrid. Both molybdenum oxide-triazole compounds displayed superior catalytic performance in comparison with the known hybrid materials [MoO₃(trz)0.5], which have different structures based on organic-inorganic perovskite-like layers. With aqueous H₂O₂ as the oxidant instead of TBHP, all compounds were completely soluble and active. A pronounced ligand influence on catalytic performance was only found for the hybrids [MoO₃(trz)0.5], and only the 1,2,4-trz compound displayed reaction-induced self-precipitation behavior. An insight into the type of solution species that may be involved in the catalytic processes with these compounds was obtained by separately treating [MoO₃(1,2,4-trz)0.5] with excess H₂O₂, which led to the crystallization of the complex (NH₄)1.8(H₃O)0.2[Mo₂O₂(μ₂-O)(O₂)₄(1,2,4-trz)]·H₂O. The single-crystal X-ray investigation of this complex reveals an oxo-bridged dinuclear structure with oxodiperoxo groups being further linked by a single triazole bridge.