How do electronegative substituents make metal complexes better catalysts for the oxidation of hydrocarbons by dioxygen?

被引：48

作者：

Bottcher, A ^{[1
]}

Birnbaum, ER ^{[1
]}

Day, MW ^{[1
]}

Gray, HB ^{[1
]}

Grinstaff, MW ^{[1
]}

Labinger, JA ^{[1
]}

机构：

[1] CALTECH, ARTHUR AMOS NOYES LAB CHEM PHYS, PASADENA, CA 91125 USA

来源：

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 1997年 / 117卷 / 1-3期

关键词：

hydrocarbon oxidation; metalloporphyrins; salen complexes;

D O I：

10.1016/S1381-1169(96)00299-3

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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.

引用

页码：229 / 242

页数：14

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