Spectroscopic Evidence for a 3d10 Ground State Electronic Configuration and Ligand Field Inversion in [Cu(CF3)4]1‿/sup>

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• 作者：Richard C. Walroth ; James T. Lukens ; Samantha N. MacMillan ; Kenneth D. Finkelstein ; Kyle M. Lancaster
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：February 17, 2016
• 年：2016
• 卷：138
• 期：6
• 页码：1922-1931
• 全文大小：640K
• ISSN：1520-5126

文摘

The contested electronic structure of [Cu(CF₃)₄]^1– is investigated with UV/visible/near IR spectroscopy, Cu K-edge X-ray absorption spectroscopy, and 1s2p resonant inelastic X-ray scattering. These data, supported by density functional theory, multiplet theory, and multireference calculations, support a ground state electronic configuration in which the lowest unoccupied orbital is of predominantly trifluoromethyl character. The consensus 3d¹⁰ configuration features an inverted ligand field in which all five metal-localized molecular orbitals are located at lower energy relative to the trifluoromethyl-centered σ orbitals.