Carbon-Oxygen Bond Formation via Organometallic Baeyer-Villiger Transformations: A Computational Study on the Impact of Metal Identity.
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...
| Publicado en: | Journal of the American Chemical Society Vol. 134; no. 4; pp. 2332 - 2340 |
|---|---|
| Autores principales: | , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
2/1/2012
|
| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=71532182&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 71532182 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 2/1/2012 vid: 134 iid: 4 pid: 997 pub: American Chemical Society artinfo: ui: 71532182 10.1021/ja2102778 ppf: 2332 ppct: 8 formats: tig: atl: Carbon-Oxygen Bond Formation via Organometallic Baeyer-Villiger Transformations: A Computational Study on the Impact of Metal Identity. aug: au: Figg, Travis M. Webb, Joanna R. Cundari, Thomas R. Gunnoe, T. Brent affil: Department of Chemistry and Center for Advanced Scientific Computing and Modeling, University of North Texas, 1155 Union Circle, #305070, Denton, Texas 76203-5017, United States Department of Chemistry, University of Virginia, McCormick Road, P.O. Box 400319, Charlottesville, Virginia 22904-4319, United States su: Chemical bonds Organometallic chemistry Chemical reactions Density functionals Chemical structure Oxidation sug: subj: Chemical bonds Organometallic chemistry Chemical reactions Density functionals Chemical structure Oxidation ab: 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. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2012 holdings: @attributes: islocal: N |
|---|