Carbon-Oxygen Bond Formation via Organometallic Baeyer-Villiger Transformations: A Computational Study on the Impact of Metal Identity

摘要

Metal-mediated formation of C-O bonds is an important transformationrnthat can occur by a variety of mechanisms. Recent studies suggest that oxygen-atomrninsertion into metal-hydrocarbyl bonds in a reaction that resembles the Baeyer-Villigerrntransformation is a viable process. In an effort to identify promising new systems, thisrnstudy is designed to assess the impact of metal identity on such O-atom insertions forrnthe reaction [(bpy)_xM(Me)(OOH)]~n → [(bpy)_xM(Ome)(OH)]~n (x = 1 or 2; bpy =rn2,2'-bipyridyl; n is varied to maintain the d-electron count at d~6 or d~8). Six d~8-square-rnplanar complexes (M = Pt~Ⅱ, Pd~Ⅱ, Ni~Ⅱ, Ir~Ⅰ, Rh~Ⅰ, and Co~Ⅰ) and eight d~6-octahedral systemsrn(M = Ir~Ⅲ, Rh~Ⅲ, Co~Ⅲ, Fe~ ⅡRu~Ⅱ, Os~Ⅱ, Mn~Ⅰ, and Tc~Ⅰ) are studied. Using density functionalrntheory calculations, the structures and energies of ground-state and transition-staternspecies are elucidated. This study shows clear trends in calculated △G~￠ for the O-atom insertions. The organometallic Baeyer-rnVilliger insertions are favored by lower coordination numbers {x = 1 versus x = 2), earlier transition metals, and first-row (3d)rntransition metals.