Counter‐Intuitive Gas‐Phase Reactivities of [V(2)](+) and [V(2)O](+) towards CO(2) Reduction: Insight from Electronic Structure Calculations

[V(2)O](+) remains “invisible” in the thermal gas‐phase reaction of bare [V(2)](+) with CO(2) giving rise to [V(2)O(2)](+); this is because the [V(2)O](+) intermediate is being consumed more than 230 times faster than it is generated. However, the fleeting existence of [V(2)O](+) and its involvement in the [V(2)](+) → [V(2)O(2)](+) chemistry are demonstrated by a cross‐over labeling experiment with a 1:1 mixture of C(16)O(2)/C(18)O(2), generating the product ions [V(2) (16)O(2)](+), [V(2) (16)O(18)O](+), and [V(2) (18)O(2)](+) in a 1:2:1 ratio. Density functional theory (DFT) calculations help to understand the remarkable and unexpected reactivity differences of [V(2)](+) versus [V(2)O](+) towards CO(2).