Covalency in Metal鈥揙xygen Multiple Bonds Evaluated Using Oxygen K-edge Spectroscopy and Electronic Structure Theory

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• 作者：Stefan G. Minasian ; Jason M. Keith ; Enrique R. Batista ; Kevin S. Boland ; Joseph A. Bradley ; Scott R. Daly ; Stosh A. Kozimor ; Wayne W. Lukens ; Richard L. Martin ; Dennis Nordlund ; Gerald T. Seidler ; David K. Shuh ; Dimosthenis Sokaras ; Tolek Tyliszczak ; Gregory L. Wagner ; Tsu-Chein Weng ; Ping Yang
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：February 6, 2013
• 年：2013
• 卷：135
• 期：5
• 页码：1864-1871
• 全文大小：458K
• 年卷期：v.135,no.5(February 6, 2013)
• ISSN：1520-5126

文摘

Advancing theories of how metal鈥搊xygen bonding influences metal oxo properties can expose new avenues for innovation in materials science, catalysis, and biochemistry. Historically, spectroscopic analyses of the transition metal MO₄^{x鈥?/sup> anions have formed the basis for new M鈥揙 bonding theories. Herein, relative changes in M鈥揙 orbital mixing in MO₄2鈥?/sup> (M = Cr, Mo, W) and MO₄鈥?/sup> (M = Mn, Tc, Re) are evaluated for the first time by nonresonant inelastic X-ray scattering, X-ray absorption spectroscopy using fluorescence and transmission (via a scanning transmission X-ray microscope), and time-dependent density functional theory. The results suggest that moving from Group 6 to Group 7 or down the triads increases M鈥揙 e* (蟺*) mixing; for example, it more than doubles in ReO₄鈥?/sup> relative to CrO₄2鈥?/sup>. Mixing in the t₂* orbitals (蟽*鈥?鈥壪€*) remains relatively constant within the same Group, but increases on moving from Group 6 to Group 7. These unexpected changes in orbital energy and composition for formally isoelectronic tetraoxometalates are evaluated in terms of periodic trends in d orbital energy and radial extension.}