文摘
To test recent computational studies on the mechanism of metal oxide cluster anion reactions with water [Ramabhadran, R. O.; et al. J. Phys. Chem. Lett. 2010, 1, 3066; Ramabhadran, R. O.; et al. J. Am. Chem. Soc. 2013, 135, 17039], the reactivity of molybdenum oxo鈥揷luster anions, MoxOy鈥?/sup> (x = 1 鈥?4; y 鈮?3x) toward both methanol (MeOH) and ethanol (EtOH) has been studied using mass spectrometric analysis of products formed in a high-pressure, fast-flow reactor. The size-dependent product distributions are compared to previous MoxOy鈥?/sup> + H2O/D2O reactivity studies, with particular emphasis on the Mo2Oy鈥?/sup> and Mo3Oy鈥?/sup> series. In general, sequential oxidation, MoxOy鈥?/sup> + ROH 鈫?MoxOy+1鈥?/sup> + RH, and addition reactions, MoxOy鈥?/sup> + ROH 鈫?MoxOy+1RH鈥?/sup>, largely corresponded with previously studied MoxOy鈥?/sup> + H2O/D2O reactions [Rothgeb, D. W., Mann, J. E., and Jarrold, C. C. J. Chem. Phys. 2010, 133, 054305], though with much lower rate constants than those determined for MoxOy鈥?/sup> + H2O/D2O reactions. This finding is consistent with the computational studies that suggested that 鈭扝 mobility on the cluster鈥搘ater complex was an important feature in the overall reactivity. There were several notable differences between cluster鈥?i>ROH and cluster鈥搘ater reactions associated with lower R鈥揙H bond dissociation energies relative to the HO鈥揌 dissociation energy.