Aerobic oxyfunctionalization is an important oxidative reaction that has been intensively studied in biological and synthetic chemistry. While numerous efforts have been focused on nickel dioxygenases and their model systems in order to probe the mechanism of dioxygen activation, little is known about the analogous pathway at organometallic nickel complexes, which are proposed to involve key high-valent Ni intermediates. In this study, we designed a new ligand scaffold to interrogate the fundamental questions of the aerobic oxygen atom transfer reaction at organonickel species and its potential application in catalytic C-H hydroxylation transformations.