Nickel–Carbon Bond Oxygenation with Green Oxidants via High-Valent Nickel Species

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Described herein is the synthesis of the NiII complex (tBuMe₂tacn)NiII(cycloneophyl) (tBuMe₂tacn = 1-tert-butyl-4,7-dimethyl-1,4,7-triazacyclononane, cycloneophyl = -CH₂CMe₂-o-C₆H₄-) and its reactivity with dioxygen and peroxides. The new tBuMe₂tacn ligand is designed to enhance the oxidatively induced bond-forming reactivity of high-valent Ni intermediates. Tunable chemoselectivity for Csp²-O vs Csp²-Csp³ bond formation was achieved by selecting the appropriate solvent and reaction conditions. Importantly, the use of cumene hydroperoxide and meta-chloroperbenzoic acid suggests a heterolytic O-O bond cleavage upon reaction with (tBuMe₂tacn)NiII(cycloneophyl). Mechanistic studies using isotopically labeled H₂O₂ support the generation of a high-valent Ni-oxygen species via an inner-sphere mechanism and subsequent reductive elimination to form the Csp²-O bond. Kinetic studies of the exceptionally fast Csp²-O bond-forming reaction reveal a first-order dependence on both (tBuMe₂tacn)NiII(cycloneophyl) and H₂O₂, and thus an overall second-order reaction. Eyring analysis further suggests that the oxidation of the NiII complex by H₂O₂ is the rate-determining step, which can be modulated by the presence of coordinating solvents. Moreover, computational studies fully support the conclusions drawn from experimental results. Overall, this study reveals for the first time the ability to control the oxidatively induced C-C vs C-O bond formation reactions at a Ni center. Importantly, the described system merges the known organometallic reactivity of Ni with the biomimetic oxidative transformations resembling oxygenases and peroxidases, and involving high-valent metal-oxygen intermediates, which is a novel approach that should lead to unprecedented oxidative catalytic transformations.