Gas-phase reactivity of heterobinuclear oxometalate anions [CrMoO 6(OR)]-, [CrWO6(OR)]-, and [MoWO6(OR)]- (R = H, nBu)

Abstract

Heterobinuclear oxometalate anions based upon [CrMoO7] 2-, [CrWO7]2-, and [MoWO7] 2- were generated and transferred to the gas phase by the electrospray process from acetonitrile solutions containing two of the salts (Bu4N)2[MO4] (M = Cr, Mo, W). Their reactivities were examined and compared with those of the related homobinuclear anions based upon [M2O7]2- (M = Cr, Mo, W). Particular emphasis was placed upon reactions relevant to gas-phase catalytic cycles described previously for oxidation of alcohols by [Mo2O 6(OH)]- (Waters, T.; O'Hair, R. A. J.; Wedd, A. G. J. Am. Chem. Soc. 2003, 125, 3384-3396). The protonated anions [MM′O 6(OH)]- each reacted with methanol with loss of water to form ..