Dual activation of CO ₂ and N ₂ facilitated by single Ta ₄ ⁺ clusters

Governing molecular activation and reaction selectivity is a fundamental strategy for advancing catalytic performance. Metal clusters show great promise for tailoring reactions due to their unique electronic structures, yet the microscopic mechanisms of how their active sites cooperate are still not fully elucidated. This work examines the reactivity of Ta _<i>n</i> ⁺ clusters with CO₂ and N₂, demonstrating the dual activation of CO₂ and N₂ by individual Ta₄ ⁺ clusters, resulting in N-O coupling. Through electron localisation function (ELF) and multi-centre bonding analyses, we elucidate how delocalised electrons and charge distribution of such metal clusters govern the reaction selectivity and stabilise intermediates along the reaction pathways. This work enhances our comprehension of cluster catalysis and offers a framework to design efficient catalysts for dual activation of CO₂ and N₂.