Mechanism of Nitrous Oxide Activation in C(sp²)-O Bond Formation Reactions Catalyzed by Nickel Complexes

Recent groundbreaking experimental reports demonstrated that Ni complexes bearing a bidentate- or tridentate-bipyridine-based ligand can be used to activate N₂O for use as an O-transfer agent in C(sp²)-O bond formation reactions under mild experimental conditions. In this work, quantum chemical calculations are used to shed light on the mechanism through which such metal complexes catalytically activate nitrous oxide, providing new fundamental insights into the development of novel catalysts for N₂O revalorization. As a case study, we consider the recent work by Cornella and co-workers (Nature, 2022, 604, 677) concerning the synthesis of phenols from aryl halides at room temperature, which requires the use of an external reducing agent. Our results suggest that the metal center remains in its Ni(II) oxidation state throughout the whole catalytic cycle, despite the presence of various redox steps in the mechanism and the Ni ability to maneuver between a number of oxidation states. This counterintuitive behavior is made possible by the ligand redox activity in the catalytic process, which involves accepting electrons from the reducing agent. Several possible pathways are systematically investigated, each associated with distinct activation modes, kinetics, and reaction outcomes. The governing factors in dictating the preferred path lie in the electronic nature of the ligand (strong vs weak field) and its geometric structure (specifically, the number of coordinating arms). These characteristics play a pivotal role in determining whether the process follows a catalytic or stoichiometric route and can be in principle modulated for the design of new metal complexes with tailored redox properties and reactivity.