Anodic oxidation of molybdenum and tungsten in alcohols: isolation and X-ray single-crystal study of side products

Abstract

The study of the side products of the anodic dissolution of molybdenum and tungsten metals in alcohols in the presence of LiCl showed them to be [LiMo2O2(OMe)7(MeOH)] 1 in the case of MeOH and [LiMo2O4(OEt)5(EtOH)] 2 in EtOH. Treatment of 2 with an excess of PriOH gave [LiMo2O4(OPri)5(PriOH)] 3, the structure of which was confirmed by a study of [{LiMo2O4(OPri)4(OC2H4OMe)}2] 4, the product of partial substitution of OR groups in 3 by 2-methoxyethoxide ligands. Reaction of 2 with an excess of MeOC2H4OH led to an equimolar mixture of [MoO2(OC2H4OMe)2] and [LiMoO2(OC2H4OMe)3] 5. In PriOH a crystalline product identified as [Mo6O10(OPri)12] 6 was isolated. Anodic oxidation of tungsten in MeOH gave a mixture of homometallic W(OMe)6 and [WO(OMe)4]. Electrosynthesis in EtOH gave as major product an amorphous glass-like mass {after separation of crystalline [WO(OEt)4] by filtration and subsequent drying of the filtrate in vacuo}. Treatment of the latter with an excess of HOC2H4OMe led to crystallization of [{LiWO2(OC2H4OMe)3}2· 2Li(HOC2H4OMe)2]2+[W6O19]2– 7. Complexes 1, 4 and 7 were characterized by X-ray single-crystal studies. A GLC-mass spectrometric study of the composition of organic side products indicated that the processes were associated with formation of ethers, alkyl halides, aldehydes or ketones and their derivatives. The nature of the possible side reactions was deduced on the basis of the data obtained.