Nickel–Carbon Bond Oxygenation with Green Oxidants via High-Valent Nickel Species
Chi‐Herng Hu, Seoung‐Tae Kim, Mu‐Hyun Baik, Liviu M. Mirica
Abstract
Described herein is the synthesis of the Ni II complex ( t BuMe 2 tacn)Ni II (cycloneophyl) ( t BuMe 2 tacn = 1- tert -butyl-4,7-dimethyl-1,4,7-triazacyclononane, cycloneophyl = −CH 2 CMe 2 - o -C 6 H 4 −) and its reactivity with dioxygen and peroxides. The new t BuMe 2 tacn ligand is designed to enhance the oxidatively induced bond-forming reactivity of high-valent Ni intermediates. Tunable chemoselectivity for Csp 2 –O vs Csp 2 –Csp 3 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 ( t BuMe 2 tacn)Ni II (cycloneophyl). Mechanistic studies using isotopically labeled H 2 O 2 support the generation of a high-valent Ni-oxygen species via an inner-sphere mechanism and subsequent reductive elimination to form the Csp 2 –O bond. Kinetic studies of the exceptionally fast Csp 2 –O bond-forming reaction reveal a first-order dependence on both ( t BuMe 2 tacn)Ni II (cycloneophyl) and H 2 O 2, and thus an overall second-order reaction. Eyring analysis further suggests that the oxidation of the Ni II complex by H 2 O 2 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.