Carbon鈥揙xygen Bond Formation via Organometallic Baeyer鈥揤illiger Transformations: A Computational Study on the Impact of Metal Identity

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• 作者：Travis M. Figg ; Joanna R. Webb ; Thomas R. Cundari ; T. Brent Gunnoe
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：February 1, 2012
• 年：2012
• 卷：134
• 期：4
• 页码：2332-2339
• 全文大小：514K
• 年卷期：v.134,no.4(February 1, 2012)
• ISSN：1520-5126

文摘

Metal-mediated formation of C鈥揙 bonds is an important transformation that can occur by a variety of mechanisms. Recent studies suggest that oxygen-atom insertion into metal鈥揾ydrocarbyl bonds in a reaction that resembles the Baeyer鈥揤illiger 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 鈫?[(bpy)_xM(OMe)(OH)]ⁿ (x = 1 or 2; bpy = 2,2鈥?bipyridyl; n is varied to maintain the d-electron count at d⁶ or d⁸). Six d⁸-square-planar complexes (M = Pt^II, Pd^II, Ni^II, Ir^I, Rh^I, and Co^I) and eight d⁶-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 螖G鈥檚 for the O-atom insertions. The organometallic Baeyer鈥揤illiger insertions are favored by lower coordination numbers (x = 1 versus x = 2), earlier transition metals, and first-row (3d) transition metals.