Oxoperoxo molybdenum(VI)- and tungsten(VI) complexes with 1-(2′-hydroxyphenyl) ethanone oxime: Synthesis, structure and catalytic uses in the oxidation of olefins, alcohols, sulfides and amines using H2O2 as a terminal oxidant

High yield synthesis of two new oxodiperoxo-molybdate, PPh4[MoO(O2)2(HPEOH)] (1), and -tungstate, PPh4[WO(O2)2(HPEOH)] (2), complexes with 1-(2′-hydroxyphenyl) ethanone oxime (HPEOH2) as organic ligand has been achieved by adding methanol solution of the ligand to the pale-yellow solution obtained by dissolving molybdic-/tungstic-acid (freshly prepared) in hydrogen peroxide and precipitating the complexes using tetraphenylphosphonium chloride. The orange-yellow complexes have been characterized by elemental analysis, IR, 1H NMR, UV–Vis spectroscopy and finally by X-ray structure analysis. Both the complexes function as facile olefin epoxidation catalysts with hydrogen peroxide as terminal oxidant and bicarbonate as a co-catalyst at room temperature. Catalytic potentiality of 1 and 2 is also exhibited in the case of oxidation of alcohols, amines and sulfides. The catalysts are very much efficient especially in olefin epoxidation giving high yield, TON (turnover number) and TOF (turnover frequency). The method described is environmentally benign and cost-effective in all the cases.

Graphical abstractHigh yield synthesis of two new oxodiperoxo-molybdate, PPh4[MoO(O2)2(HPEOH)] (1) and -tungstate, PPh4[WO(O2)2(HPEOH)] (2) complexes with 1-(2′-hydroxyphenyl) ethanone oxime (HPEOH2) as organic ligand has been achieved by adding methanol solution of the ligand to the orange red solution obtained by dissolving molybdic-/tungstic-acid (freshly prepared) in hydrogen peroxide and precipitating the complexes using tetraphenylphosphonium chloride. The complexes have been characterized by elemental analysis, IR, 1H NMR, UV–Vis spectroscopy and finally by X-ray structure analysis. Both the complexes function as facile olefin epoxidation catalysts with hydrogen peroxide as terminal oxidant and bicarbonate as a co-catalyst at room temperature. Catalytic potentiality of 1 and 2 is also exhibited in the case of oxidation of alcohols, amines and sulfides. The catalysts are very much efficient especially in olefin epoxidation giving high yield, TON (turnover number) and TOF (turnover frequency). The method described is environmentally benign and cost effective in all the cases.Figure optionsDownload full-size imageDownload as PowerPoint slide