Highly soluble dichloro, dibromo and dimethyl dioxomolybdenum(VI)-bipyridine complexes as catalysts for the epoxidation of olefins

Abstract

The reaction of solvent substituted MoO 2X 2(S) 2 (X = Cl, S = THF; X = Br, S = DMF) complexes with one equivalent of bidentate nitrogen donor ligands at room temperature leads within a few minutes to the quantitative formation of complexes of the type [MoO 2X 2L 2] (L = 4,4′-bis-methoxycarbonyl-2,2′-bipyridine, 5,5′-bis-methoxycarbonyl-2,2′-bipyridine, 4,4′-bis-ethoxycarbonyl-2,2′-bipyridine, 5,5′-bis-ethoxycarbonyl-2,2′-bipyridine). Treatment of the complexes [MoO 2Cl 2L 2] with Grignard reagents at low temperatures yields dimethylated complexes of the formula [MoO 2(CH 3) 2L 2]. [MoO 2Br 2(4,4′-bis-ethoxycarbonyl-2,2′-bipyridine)], [MoO 2Br 2(5,5′-bis-methoxycarbonyl-2,2′-bipyridine)] and [MoO 2Br 2(5,5′-bis-ethoxycarbonyl-2,2′-bipyridine)] have been exemplary examined by single crystal X-ray analysis. The complexes were applied as homogenous catalysts for the epoxidation of cyclooctene with tert-butyl hydroperoxide (TBHP) as oxidising agent under solvent-free conditions. The complexes containing L = Cl have been additionally investigated with room temperature ionic liquids (RTILs) as solvents. The catalytic activity of the [MoO 2X 2L 2] complexes in olefin epoxidation with tert-butyl hydroperoxide is on average very good. The main advantage of the synthesised complexes in comparison to previously reported complexes is their high solubility. This good solubility is apparently the reason that the catalytic potential of the compounds can unfold. The turnover frequencies (TOFs) in RTILs are even higher, showing the performance of the catalysts under optimised conditions.