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

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Article discussing a computational study on the impact of metal identity and carbon-oxygen bond formation via organometallic Baeyer-Villiger transformations.

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8 p.

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Figg, Travis M.; Webb, Joanna R.; Cundari, Thomas R., 1964- & Gunnoe, T. Brent December 20, 2011.

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Article discussing a computational study on the impact of metal identity and carbon-oxygen bond formation via organometallic Baeyer-Villiger transformations.

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8 p.

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Reprinted with permission from the Journal of the American Chemical Society. Copyright 2012 American Chemical Society.

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.

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  • Journal of the American Chemical Society, 2012, Washington D.C.: American Chemical Society, pp. 2332-2339

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 134
  • Issue: 4
  • Page Start: 2332
  • Page End: 2339
  • Peer Reviewed: Yes

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UNT Scholarly Works

The Scholarly Works Collection is home to materials from the University of North Texas community's research, creative, and scholarly activities and serves as UNT's Open Access Repository. It brings together articles, papers, artwork, music, research data, reports, presentations, and other scholarly and creative products representing the expertise in our university community. Access to some items in this collection may be restricted.

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  • December 20, 2011

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  • Oct. 9, 2012, 10:02 a.m.

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  • Jan. 9, 2015, 5:10 p.m.

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Figg, Travis M.; Webb, Joanna R.; Cundari, Thomas R., 1964- & Gunnoe, T. Brent. Carbon-Oxygen Bond Formation via Organometallic Baeyer-Villiger Transformations: A Computational Study on the Impact of Metal Identity, article, December 20, 2011; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc107789/: accessed April 28, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.