Reactivity of Neutral Tantalum Sulfide Clusters Ta₃S (n = 0-4) with N₂

Nitrogen (N₂) fixation is a challenging and vital issue in chemistry. Inspired by the fact that the active sites of nitrogenases are polynuclear metal sulfide clusters, the reactivity of gas-phase metal sulfide clusters toward N₂ has received considerable attention to gain fundamental insights into nitrogen fixation. Herein, neutral tantalum sulfide clusters have been prepared and their reactivity toward N₂ has been investigated by mass spectrometry in conjunction with density functional theory (DFT) calculations. The experimental results showed that Ta₃S (n = 0-3) could adsorb N₂, while Ta₃S₄ was inert to N_2. The DFT calculations revealed that the complete cleavage of the N≡N bond on the trinuclear metal center in the Ta₃S_0-3/N₂ reaction systems was overall barrierless under thermal collision conditions. The sulfur ligands can facilitate the approaching of N₂ toward the metal center but weaken the electron-donating ability of the metal center. The inertness of Ta₃S₄ is ascribed to the electron-deficient state of Ta₃ in Ta₃S₄ and the least effective orbital interaction in the Ta₃S₄/N₂ couple. This study provides new insights into the ligand effect on the interaction of the metal clusters with N_2.