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)(x)M(Me)(OOH)](n) --> [(bpy)(x)M(OMe)(OH)](n) (x = 1 or 2; bpy = 2,2'-bipyridyl; n is varied to maintain the d-electron count at d(6) or d(8)). Six d(8)-square-planar complexes (M = Pt-II, Pd-II, Ni-II, Ir-II, Rh-I, and Co-I) and eight d(6)-octahedral systems (M = Ir-III, Rh-III, Co-III, Fe-III Ru-II, Os-II, Mn-I, and Tc-I) 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 Delta G double dagger's for the 0-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.