Date: December 20, 2011
Creator: Figg, Travis M.; Webb, Joanna R.; Cundari, Thomas R., 1964- & Gunnoe, T. Brent
Description: This article discusses a computational study on the impact of metal identity. Abstract: 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)ₓM(Me)(OOH)]ⁿ → [(bpy)ₓM(OMe)(OH)]ⁿ (x = 1 or 2; bpy = 2,2'-bipyridyl; n is varied to maintain the d-electron count at d⁶ or d⁸). Six d⁸-square-planar complexes (M = Ptᴵᴵ, Pdᴵᴵ, Niᴵᴵ, Irᴵ, Rhᴵ, and Coᴵ) and eight d⁶-octahedral systems (M = Irᴵᴵᴵ, Rhᴵᴵᴵ, Coᴵᴵᴵ, Feᴵᴵ, Ruᴵᴵ, Osᴵᴵ, Mnᴵ, and Tcᴵ) 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 ∆G‡'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.
Contributing Partner: UNT College of Arts and Sciences