How do electronegative substituents make metal complexes better catalysts for the oxidation of hydrocarbons by dioxygen?
How do electronegative substituents make metal complexes better catalysts for the oxidation of hydrocarbons by dioxygen?
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DOI：
10.1016/s1381-1169(96)00299-3
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发表时间：
1997-03-14
影响因子：
--
通讯作者：
Labinger, JA
中科院分区：
文献类型：
--
作者：
Bottcher, A;Birnbaum, ER;Labinger, JA
模拟研究支持自由基链的自氧化机制的异丁烷的好氧氧化卤化卟啉铁配合物催化。电负性卤素取代基的关键作用是增加Fe-III/（II）氧化还原电位，从而加速中间体叔丁基过氧化氢被（porph）Fe-III氧化。电负性取代的Salen铁配合物的电子结构已被表征的几种技术，并与催化氧化环己烯的活性的变化。报道了[Fe（（NO2）（4）salen）（H2O）Cl]的晶体和分子结构。
Modeling studies support a radical-chain autoxidation mechanism for the aerobic oxidation of isobutane catalyzed by halogenated porphyrin iron complexes. A key role of the electronegative halogen substituents is to increase the Fe-III/(II) redox potential and thereby accelerate oxidation of the intermediate t-butyl hydroperoxide by (porph)Fe-III. The electronic structures of electronegatively substituted salen iron complexes have been characterized by several techniques, and related to changes in catalytic activity for oxidation of cyclohexene. The crystal and molecular structure of [Fe((NO2)(4)salen)(H2O)Cl] is reported.