Abstract
A series of vanadium and phosphorus heteronuclear oxide cluster cations (V(x)P(y)O(z)(+)) are prepared by laser ablation and the reactions of V(3)PO(10)˙(+) and V(4)O(10)˙(+) with methane in a fast flow reactor under the same conditions are studied. A time of flight mass spectrometer is used to detect the cluster distribution before and after reactions. In addition to previously identified reaction of V(4)O(10)˙(+) + CH(4)→ V(4)O(10)H(+) + CH(3)˙, the observation of hydrogen atom pickup cluster V(3)PO(10)H(+) suggests the reaction: V(3)PO(10)˙(+) + CH(4)→ V(3)PO(10)H(+) + CH(3)˙. The rate of the reaction of V(4)O(10)˙(+) with CH(4) is approximately 2.5 times faster than that of V(3)PO(10)˙(+) with CH(4). Density functional theory (DFT) calculations predict that structure of V(3)PO(10)˙(+) is topologically similar to that of V(4)O(10)˙(+), as well as that of P(4)O(10)˙(+), which is very similar to V(4)O(10)˙(+) in terms of methane activation in previous studies. The facile methane activation by the homo- and hetero-nuclear oxide clusters can all be attributed to the presence of an oxygen-centered radical (O˙) in these clusters. Further theoretical study indicates that the O˙ radical (or spin density of the cluster) can transfer within the high symmetry V(4)O(10)˙(+) and P(4)O(10)˙(+) clusters quite easily, and CH(4) molecule further enhances the rate of intra-cluster spin density transfer. In contrast, the intra-cluster spin density transfer within low symmetry V(3)PO(10)˙(+) is thermodynamically forbidden. The experimentally observed reactivity difference is consistent with the theoretical consideration of the intra-cluster spin density transfer.
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