Side‐on‐End‐on Coordination of Dinitrogen on a Polynuclear Vanadium Nitride Cluster Anion [V5N5]−.

The side‐on‐end‐on coordination of N2 can be very important to activate and functionalize this very stable molecule. However, such coordination has rarely been reported. This study reports a gas‐phase species (a polynuclear vanadium nitride cluster anion [V5N5]−) that can capture N2 efficiently (12 %), and the quantum chemistry modelling suggests an unusual side‐on‐end‐on coordination. The cluster anions were generated by laser ablation and the reaction with N2 has been characterized by mass spectrometry, photoelectron imaging spectroscopy, and density functional theory calculations. The back‐donation interactions between the localized d–d bonding orbitals on the low‐coordinated dual metal (V) sites and the antibonding π* orbitals of N2 are the driving forces to adsorb N2 with a high binding energy (about 2.0 eV). [ABSTRACT FROM AUTHOR]