1H-ENDOR Evidence for a Hydrogen-Bonding Interaction That Modulates the Reactivity of a Nonheme FeIV鈺怬 Unit

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• 作者：Muralidharan Shanmugam ; Genqiang Xue ; Lawrence Que ; Jr. ; Brian M. Hoffman
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：October 1, 2012
• 年：2012
• 卷：51
• 期：19
• 页码：10080-10082
• 全文大小：233K
• 年卷期：v.51,no.19(October 1, 2012)
• ISSN：1520-510X

文摘

We report that a novel use of 35 GHz ¹H-ENDOR spectroscopy establishes the presence in 1 of an Fe^IV鈺怬路路路H鈥揙鈥揊e^III hydrogen bond predicted by density functional theory computations to generate a six-membered-ring core for 1. The hydrogen bond rationalizes the difference in the C鈥揌 bond cleavage reactivity between 1 and 4(OCH₃) (where a CH₃O group has replaced the HO on the Fe^III site). This result substantiates the seemingly paradoxical conclusion that the nonheme Fe^IV鈺怬 unit of 1 not only has the electrophilic character required for H-atom abstraction but also retains sufficient nucleophilic character to accept a hydrogen bond from the Fe^III鈥揙H unit.