A Facile N≡N Bond Cleavage by the Trinuclear Metal Center in Vanadium Carbide Cluster Anions V 3 C 4 .

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 N ₂ and subsequent C-N coupling on trinuclear carbide cluster anions V ₃ C ₄ ^- 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 N ₂ bonded with the V ₃ 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 N ₂ 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 N ₂ . Furthermore, carbon ligands also play a considerable role in enhancing the reactivity of the metal core toward N ₂ . This study strongly suggests a new mechanism of N≡N bond cleavage by gas-phase metal clusters.