| Sumario: | Metal-mediated formation of C-O bonds is an important transformation that can occur by a variety of mechanisms. Recent studies suggest that oxygen-atom insertion into metal-hydrocarbyl bonds in a reaction that resembles the Baeyer-Villiger transformation is a viable process. In an effort to identify promising new systems, this study is designed to assess the impact of metal identity on such O-atom insertions for the reaction [(bpy)M(Me)(OOH)] → [(bpy)M(OMe)(OH)] (x = 1 or 2; bpy = 2,2'-bipyridyl; n is varied to maintain the d-electron count at d or d). Six d-square-planar complexes (M = Pt, Pd, Ni, Ir, Rh, and Co) and eight d-octahedral systems (M = Ir, Rh, Co, Fe Ru, Os, Mn, and Tc) are studied. Using density functional theory calculations, the structures and energies of ground-state and transition-state species are elucidated. This study shows clear trends in calculated ΔG's for the O-atom insertions. The organometallic Baeyer-Villiger insertions are favored by lower coordination numbers (x = 1 versus x = 2), earlier transition metals, and first-row (3d) transition metals.
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