Aerobic oxidation of hydrocarbons catalyzed by electronegative iron salen complexes
Aerobic oxidation of hydrocarbons catalyzed by electronegative iron salen complexes
复制标题
DOI：
10.1016/s1381-1169(96)00053-2
复制
发表时间：
1996-11-25
影响因子：
--
通讯作者：
Gray, HB
中科院分区：
文献类型：
--
作者：
Bottcher, A;Grinstaff, MW;Gray, HB
制备了许多带有电负性取代基的萨伦衍生物及其相应的铁（III）氯配合物。一些配合物催化环己烯的有氧氧化，主要是烯丙基氧化产物。证据支持自由基链自氧化机制，与复杂的功能分解中间烷基氢过氧化物。仅对具有较高Fe（III/II）还原电位的配合物观察到活性，但活性与电位的不完全相关表明，更微妙的结构和电子效应在决定催化反应速率方面也起着重要作用。
A number of salen derivatives bearing electronegative substituents and their corresponding iron(III) chloro complexes have been prepared. Several of the complexes catalyze aerobic oxidation of cyclohexene, primarily to allylic oxidation products. Evidence supports a radical chain autoxidation mechanism, with the complex functioning to decompose intermediate alkyl hydroperoxides. Activity is observed only for complexes with relatively high Fe(III/II) reduction potentials, but the incomplete correlation of activity with potential indicates that more subtle structural and electronic effects also play an important role in determining the rates of the catalytic reactions.