Facile CO bond cleavage on polynuclear vanadium nitride clusters V₄N₅

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.