X-ray Absorption Spectroscopy and Reactivity of Thiolate-Ligated FeIII−OOR Complexes

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• 作者：Jay Stasser ; Frances Namuswe ; Gary D. Kasper ; Yunbo Jiang ; Courtney M. Krest ; Michael T. Green ; James Penner-Hahn ; David P. Goldberg
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：October 18, 2010
• 年：2010
• 卷：49
• 期：20
• 页码：9178-9190
• 全文大小：1032K
• 年卷期：v.49,no.20(October 18, 2010)
• ISSN：1520-510X

文摘

The reaction of a series of thiolate-ligated iron(II) complexes [Fe^II([15]aneN₄)(SC₆H₅)]BF₄ (1), [Fe^II([15]aneN₄)(SC₆H₄-p-Cl)]BF₄ (2), and [Fe^II([15]aneN₄)(SC₆H₄-p-NO₂)]BF₄ (3) with alkylhydroperoxides at low temperature (−78 °C or −40 °C) leads to the metastable alkylperoxo-iron(III) species [Fe^III([15]aneN₄)(SC₆H₅)(OOtBu)]BF₄ (1a), [Fe^III([15]aneN₄)(SC₆H₄-p-Cl)(OOtBu)]BF₄ (2a), and [Fe^III([15]aneN₄)(SC₆H₄-p-NO₂)(OOtBu)]BF₄ (3a), respectively. X-ray absorption spectroscopy (XAS) studies were conducted on the Fe^III−OOR complexes and their iron(II) precursors. The edge energy for the iron(II) complexes (7118 eV) shifts to higher energy upon oxidation by ROOH, and the resulting edge energies for the Fe^III−OOR species range from 7121−7125 eV and correlate with the nature of the thiolate donor. Extended X-ray absorption fine structure (EXAFS) analysis of the iron(II) complexes 1−3 in CH₂Cl₂ show that their solid state structures remain intact in solution. The EXAFS data on 1a−3a confirm their proposed structures as mononuclear, 6-coordinate Fe^III−OOR complexes with 4N and 1S donors completing the coordination sphere. The Fe−O bond distances obtained from EXAFS for 1a−3a are 1.82−1.85 Å, significantly longer than other low-spin Fe^III−OOR complexes. The Fe−O distances correlate with the nature of the thiolate donor, in agreement with the previous trends observed for ν(Fe−O) from resonance Raman (RR) spectroscopy, and supported by optimized geometries obtained from density functional theory (DFT) calculations. Reactivity and kinetic studies on 1a− 3a show an important influence of the thiolate donor.