Sc3+-Triggered Oxoiron(IV) Formation from O2 and its Non-Heme Iron(II) Precursor via a Sc3+鈥揚eroxo鈥揊e3+ Intermediate

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• 作者：Feifei Li ; Katherine M. Van Heuvelen ; Katlyn K. Meier ; Eckard M眉nck ; Lawrence Que ; Jr.
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：July 17, 2013
• 年：2013
• 卷：135
• 期：28
• 页码：10198-10201
• 全文大小：300K
• 年卷期：v.135,no.28(July 17, 2013)
• ISSN：1520-5126

文摘

We report that redox-inactive Sc³⁺ can trigger O₂ activation by the Fe^II(TMC) center (TMC = tetramethylcyclam) to generate the corresponding oxoiron(IV) complex in the presence of BPh₄^{鈥?/sup> as an electron donor. To model a possible intermediate in the above reaction, we generated an unprecedented Sc3+ adduct of [FeIII(畏2-O₂)(TMC)]+ by an alternative route, which was found to have an Fe3+鈥?渭-畏2:畏2-peroxo)鈥揝c3+ core and to convert to the oxoiron(IV) complex. These results have important implications for the role a Lewis acid can play in facilitating O鈥揙 bond cleavage during the course of O₂ activation at non-heme iron centers.}