Reactions of M+ and Mo+(M = V, Nb, Ta) with methanol

The primary reactions of the transition metal cations M þ (M ¼ V, Nb and Ta) and their oxides with methanol are experimentally and theoretically investigated. Combining with the experimental results, we propose the reaction pathways of those primary reactions. The potential energy surfaces (PES) of these reactions are explored at B3LYP/Lanl2dz (for M) and 6-31g* (for C, H and O) level. The structures and properties of the complexes involving in these reactions are also theoretically studied. The calculated results show that a crossing between the high-spin and low-spin PES occurs just after TS1, which plays an important role in decreasing the barrier heights of these transition states. The theoretical results are in excellent agreement with the experimental results. q 2004 Elsevier B.V. All rights reserved.