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

Journal Article · · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja2102778· OSTI ID:1065947

Figg, Travis M. ^[1]; Webb, Joanna R. ^[2]; Cundari, Thomas R. ^[1]; Gunnoe, T. Brent ^[2]

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1. Univ. of North Texas, Denton, TX (United States). Dept. of Chemistry and Center for Advanced Scientific Computing and Modeling
2. Univ. of Virginia, Charlottesville, VA (United States). Dept. of Chemistry

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 = 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 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.

• Research Organization: Energy Frontier Research Centers (EFRC) (United States). Center for Catalytic Hydrocarbon Functionalization (CCHF)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• DOE Contract Number: SC0001298
• OSTI ID: 1065947
• Journal Information: Journal of the American Chemical Society, Vol. 134, Issue 4; Related Information: CCHF partners with University of Virginia (lead); Brigham Young University; California Institute of Technology; Colorado School of Mines; University of Maryland; University of North Carolina, Chapel Hill; University of North Texas; Princeton University; The Scripps Research Institute; Yale University; ISSN 0002-7863
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

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