Oxygen-exchange pathways in aluminum polyoxocations

Using molecular dynamics simulations and electronic structure methods, we postulate a mechanism to explain the complicated reactivity trends that are observed for oxygen isotope exchange reactions between sites in aluminum polyoxocations of the epsilon-Keggin type and bulk solution. Experimentally, the molecules have four nonequivalent oxygens that differ considerably in reactivity both within a molecule, and between molecules in the series: Al-13, GaAl12, and GeAl12 [MO4Al12(OH)(24)(H2O)(12)(n+)(aq); with M = Al(III) for Al-13, n = 7; M = Ga(III) for GaAl12, n = 7; M = Ge(IV) for GeAl12, n = 8]. We find that a partly dissociated. metastable intermediate molecule of expanded volume is necessary for exchange of both sets of mu(2)-OH and that the steady-state concentration of this intermediate reflects the bond strengths between the central metal and the mu(4)-O. Thus the central metal exerts extraordinary control over reactions at hydroxyl bridges. although these are three bonds away. This mechanism not only explains the reactivity trends for oxygen isotope exchange in mu(2)-OH and eta-OH2 sites in the epsilon-Keggin aluminum molecules, but also explains the observation that the reactivities, of minerals tend to reflect the presence of highly coordinated oxygens, such as the mu(4)-O in boehmite, alpha-, and gamma-Al2O3 and their Fe(III) analogs. The partial dissociation of these highly coordinated oxygens, coupled with simultaneous activation and displacement of neighboring metal centers, may be a fundamental process by which metals atoms undergo ligand exchanges at mineral surfaces. Copyright (C) 2004 Elsevier Ltd.