title: Carbon-oxygen bond formation via organometallic Baeyer-Villiger transformations: 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)(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(I), Rh(I), and Co(I)) and eight d(6)-octahedral systems (M = Ir(III), Rh(III), Co(III), Fe(II) 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 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.
authors.affiliation: Department of Chemistry and Center for Advanced Scientific Computing and Modeling, University of North Texas, 1155 Union Circle, #305070, Denton, Texas 76203-5017, USA.
authors.forename: Travis M
authors.initials: TM
authors.lastname: Figg
authors.forename: Joanna R
authors.initials: JR
authors.lastname: Webb
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Cundari
authors.forename: T Brent
authors.initials: TB
authors.lastname: Gunnoe
mesh_terms: D002244:Carbon / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D009942:Organometallic Compounds; D002244:Carbon; D010100:Oxygen