Conflicting Role of Water in the Activation of H2O2 and the Formation and Reactivity of Non-Heme FeIII–OOH and FeIII–O–FeIII Complexes at Room Temperature

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• 作者：Sandeep K. Padamati ; Apparao Draksharapu ; Duenpen Unjaroen ; Wesley R. Browne
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：May 2, 2016
• 年：2016
• 卷：55
• 期：9
• 页码：4211-4222
• 全文大小：784K
• 年卷期：0
• ISSN：1520-510X

文摘

The formation of an Fe^III–OOH species by reaction of complex 1 ([(MeN3Py)Fe^II(CH₃CN)₂]²⁺) with H₂O₂ at room temperature is reported and is studied by a combination of UV/vis absorption, EPR, and resonance Raman spectroscopies. The formation of the Fe^III–OOH species, and its subsequent conversion to relatively inert Fe^III–O–Fe^III species, is shown to be highly dependent on the concentration of water, with excess water favoring the formation of the latter species, which is studied by UV/vis absorption spectroelectrochemistry also. The presence of acetic acid increases the rate and extent of oxidation of 1 to its iron(III) state and inhibits the wasteful decomposition of H₂O₂ but does not affect significantly the spectroscopic properties of the Fe^III–OOH species formed.