A Facile N≡N Bond Cleavage by the Trinuclear Metal Center in Vanadium Carbide Cluster Anions V3C4.

Cleavage of the triple N≡N bond by metal clusters is of fundamental interest and practical importance in nitrogen fixation. Previous studies of N≡N bond cleavage by gas-phase metal clusters emphasized the importance of the dinuclear metal centers. Herein, the dissociative adsorption of N2 and subsequent C-N coupling on trinuclear carbide cluster anions V3C4- under thermal collision conditions have been characterized by employing mass spectrometry (collision induced dissociation), cryogenic photoelectron imaging spectroscopy, and quantum chemistry calculations. A theoretical analysis identified a crucial adsorption intermediate with N2 bonded with the V3 metal core in the end-on/side-on/side-on (ESS) mode, which most likely enables the facile cleavage of the N≡N bond. Such a vital N2 coordination in the ESS mode is a result of symmetry-matched interactions between the occupied orbitals of the metal core and both of the two empty π* orbitals of N2. Furthermore, carbon ligands also play a considerable role in enhancing the reactivity of the metal core toward N2. This study strongly suggests a new mechanism of N≡N bond cleavage by gas-phase metal clusters.