Journal article

Gas-Phase Reactions of [VO2(OH)(2)](-) and [V2O5(OH)](-) with Methanol: Experiment and Theory

Benjamin L Harris, Tom Waters, George N Khairallah, Richard AJ O'Hair

JOURNAL OF PHYSICAL CHEMISTRY A | AMER CHEMICAL SOC | Published : 2013

Abstract

The gas-phase reactivity of the vanadium hydroxides [VO(2)(OH)(2)](-) and [V(2)O(5)(OH)](-) toward methanol was examined using a combination of ion-molecule reactions (IMRs) and collision-induced dissociation (CID) in a quadrupole ion trap mass spectrometer. Isotope-labeling experiments with CD(3)OH, (13)CH(3)OH, and CH(3)(18)OH were used to confirm the stoichiometry of ions and the observed sequence of reactions. The experimental data were interpreted with the aid of density functional theory calculations, carried out at the B3LYP/SDD6-311++G** level of theory. While [VO(2)(OH)(2)](-) is unreactive, [V(2)O(5)(OH)](-) undergoes a metathesis reaction to yield [V(2)O(5)(OCH(3))](-). The DFT ca..

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Grants

Awarded by Australian Research Council


Funding Acknowledgements

We thank the Australian Research Council for financial support via Grants to T.W. (#DP0772053), G.N.K. (#DP1096134), and R.A.J.O. (#DP0558430 and the ARC CoE Program). B.L.H., T.W., and G.N.K. thank the Victorian Institute for Chemical Sciences High Performance Computing Facility for allocation of computer time. Dedicated to our friend and colleague Peter B. Armentrout on the occasion of his 60th birthday and in recognition of his outstanding work in metal-mediated chemistry, which has been an ongoing source of inspiration.