金属离子对非血红素铁(IV)-氧配合物催化硫醚氧化为亚砜过程中，由直接氧转移到金属离子偶联电子转移的机理开关的影响。
Metal ion effect on the switch of mechanism from direct oxygen transfer to metal ion-coupled electron transfer in the sulfoxidation of thioanisoles by a non-heme iron(IV)-oxo complex.
机构信息
Department of Bioinspired Science, Ewha Womans University, Seoul 120-750, Korea.
出版信息
J Am Chem Soc. 2011 Apr 13;133(14):5236-9. doi: 10.1021/ja200901n. Epub 2011 Mar 16.
PMID:21410258
Abstract
The mechanism of sulfoxidation of thioaniosoles by a non-heme iron(IV)-oxo complex is switched from direct oxygen transfer to metal ion-coupled electron transfer by the presence of Sc(3+). The switch in the sulfoxidation mechanism is dependent on the one-electron oxidation potentials of thioanisoles. The rate of sulfoxidation is accelerated as much as 10(2)-fold by the addition of Sc(3+).
摘要
非血红素铁（IV）-氧配合物催化硫醚的氧化反应的机理可通过 Sc(3+)的存在由直接氧转移转变为金属离子耦合的电子转移。氧化机制的转变取决于硫醚的单电子氧化电位。通过添加 Sc(3+)，硫醚的氧化速率可加速高达 10(2)倍。
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