Facile CO bond cleavage on polynuclear vanadium nitride clusters V4N5−

Abstract

Identifying the structural configurations of precursors for CO dissociation is fundamentally interesting and industrially important in the fields of, e.g., Fischer–Tropsch synthesis. Herein, we demonstrated that CO could be dissociated on polynuclear vanadium nitride V₄N₅⁻ clusters at room temperature, and a key intermediate, with CO in a N-assisted tilted bridge coordination where the C–O bond ruptures easily, was discovered. The reaction was characterized by mass spectrometry, photoelectron spectroscopy, and quantum-chemistry calculations, and the nature of the adsorbed CO on product V₄N₅CO⁻ was further characterized by a collision-induced dissociation experiment. Theoretical analysis evidences that CO dissociation is predominantly governed by the low-coordinated V and N atoms on the (V₃N₄)VN⁻ cluster and the V₃N₄ moiety resembles a support. This finding strongly suggests that a novel mode for facile CO dissociation was identified in a gas-phase cluster study.