Department of Chemistry , The Johns Hopkins University , 3400 North Charles Street , Baltimore , Maryland 21218 , United States.
Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science , The University of Manchester , 131 Princess Street , Manchester M1 7DN , United Kingdom.
Inorg Chem. 2019 Aug 5;58(15):9557-9561. doi: 10.1021/acs.inorgchem.9b01208. Epub 2019 Jul 17.
An iron(III) methoxide complex reacts with -substituted triarylmethyl radicals to give iron(II) and methoxyether products. Second-order rate constants for the radical derivatives were obtained. Hammett and Marcus plots suggest the radical transfer reactions proceed via a concerted process. Calculations support the concerted nature of these reactions involving a single transition state with no initial charge transfer. These findings have implications for the radical "rebound" step invoked in nonheme iron oxygenases, halogenases, and related synthetic catalysts.
三价铁甲氧基络合物与 -取代的三芳基自由基反应，生成铁(II)和甲氧基醚产物。得到了自由基衍生物的二级速率常数。Hammett 和 Marcus 图表明自由基转移反应通过协同过程进行。计算支持这些反应的协同性质，涉及没有初始电荷转移的单个过渡态。这些发现对非血红素铁加氧酶、卤代酶和相关合成催化剂中涉及自由基“回弹”步骤的反应有影响。
