MECHANISM OF CATALYTIC OXYGENATION OF ALKANES BY HALOGENATED IRON PORPHYRINS

被引：329

作者：

GRINSTAFF, MW ^{[1
]}

HILL, MG ^{[1
]}

LABINGER, JA ^{[1
]}

GRAY, HB ^{[1
]}

机构：

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

来源：

SCIENCE | 1994年 / 264卷 / 5163期

关键词：

D O I：

10.1126/science.8191283

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Halogenation of an iron porphyrin causes severe saddling of the macrocyclic structure and a large positive shift in the iron(III)/(II) redox couple. Although perhalogenated iron(II) porphyrins such as Fe(TFPPBr8) [H2TFPPBr8, beta-octabromo-tetrakis(pentafluorophenyl)-porphyrin] are relatively resistant to autoxidation, they rapidly reduce alkyl hydroperoxides. These and related reactivity studies suggest that catalysis of alkane oxygenation by Fe(TFPPBr8)Cl occurs through a radical-chain mechanism in which the radicals are generated by oxidation and reduction of alkyl hydroperoxides.

引用

页码：1311 / 1313

页数：3

共 29 条

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