Counter‐Intuitive Gas‐Phase Reactivities of [V₂]⁺ and [V₂O]⁺ towards CO₂ Reduction: Insight from Electronic Structure Calculations

Abstract

[V2O]+ remains “invisible” in the thermal gas‐phase reaction of bare [V2]+ with CO2 giving rise to [V2O2]+; this is because the [V2O]+ intermediate is being consumed more than 230 times faster than it is generated. However, the fleeting existence of [V2O]+ and its involvement in the [V2]+ → [V2O2]+ chemistry are demonstrated by a cross‐over labeling experiment with a 1:1 mixture of C16O2/C18O2, generating the product ions [V216O2]+, [V216O18O]+, and [V218O2]+ in a 1:2:1 ratio. Density functional theory (DFT) calculations help to understand the remarkable and unexpected reactivity differences of [V2]+ versus [V2O]+ towards CO2.

Oxidative Addition of Dihydrogen to Divanadium in Solid Ne: Multiple‐Bonded Triplet HVVH and Singlet V2(μ‐H)2

“…[25] Interestingly,v ery recently, the reaction of V 2 + with CO 2 to yield V 2 O 2 + has been investigated, and the surprising observation has been made that the intermediate V 2 O + reacts considerably faster than V 2 + . [26] In this work, it is shown by IR spectroscopy that neutral V 2 reacts with H 2 without as ignificant reaction barrier to linear HVVH under preservation of the spin multiplicity and to the V 2 (m-H) 2 isomer with anonplanar,folded structure (see Figure 1). Thel atter is generated, in particular,u pon irradiation with light of aw avelength in the ultraviolet range between 250 and 385 nm.…”