DFT study of the water-assisted tautomerization process between hydrated oxide, MO(H2O)(+), and dihydroxide, M(OH)(2)(+) cations (M = V, Nb and Ta)

Density functional theory (DFT) calculations point out that the participation of water can effectively lower the barrier height for the isomerization process between hydrated oxide cation, MO(H2O)(+), and dihydroxide cation, M(OH)(2)(+), (M = V, Nb and Ta). The catalytic effect is achieved by a water-assisted mechanism in which water acts as proton donor and acceptor, via a transition structure corresponding to a six-membered ring. In the case of vanadium atom, the presence of two water molecules has been taken into account and the tautomerization becomes nearly barrierless, decreasing both the stability of the transition structures relative to intermediates and the depths of wells associated with the intermediates. (C) 2003 Elsevier B.V. All rights reserved.

DFT study of the reaction between VO2+ and C2H6

The molecular mechanisms of the reaction VO2+ ((1)A(1)/(3)A'') + C2H6 ((1)A(g)) to yield V(OH)(2)(+) ((1)Sigma(+)/(3)Sigma(-)) + C2H4 ((1)A(g)) and/or VO+ ((1)Delta/(3)Sigma) + H2O ((1)A(1)) + C2H4 (Ag-1) have been investigated with density functional theory (DFT) at the B3LYP/6-311G(2d,p) level. Calculations including geometry optimization, vibrational analysis, and Gibbs free energy for the stationary points on the reactive potential energy surfaces at both the singlet (s) and first excited triplet (t) electronic states have been carried out. The most thermodynamically and kinetically favorable pathway is the formation of t-V(OH)(2)(+) + C2H4 along a four-step molecular mechanism (insertion, two consecutive hydrogen transfers, and elimination). A crossing point between s and t electronic states has been characterized. A comparison with previous works on VO2+ + C2H4 (Gracia et al. J. Phys. Chem. A 2003, 107, 3107-3120) and VO2+ + C3H8 (Engeser et al. Organometallics 2003, 22, 3933-3943) reactions allows us a rationalization of the different reactivity patterns. The catalytic role of water molecules in the tautomerization process between hydrated oxide cation, VO(H2O)(+,) and dihydroxide cation, V(OH)(2)(+), is achieved by a water-assisted mechanism.