Oxidation of Cyclohexane by a High-Valent Iron Bispidine Complex: A Combined Experimental and Computational Mechanistic Study

被引：51

作者：

Comba, Peter ^{[1
]}

Maurer, Martin ^{[1
]}

Vadivelu, Prabha ^{[1
]}

机构：

[1] Heidelberg Univ, Inst Anorgan Chem, D-69120 Heidelberg, Germany

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2008年 / 112卷 / 50期

关键词：

D O I：

10.1021/jp8037895

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：

Experimental data suggest that there are various competing pathways for the catalytic and stoichiometric oxygenation of cyclohexane, assisted by iron-bispidine complexes and using various oxidants (H2O2, O-2, PhIO). Density functional theory calculations indicate that both Fe-IV=O and Fe-V=O species are accessible and efficiently transfer their oxygen atoms to cyclohexane. The reactivities of the two isomers each and the two possible spin states for the Fe-IV=O and Fe-V=O species are sufficiently different to allow an interpretation of the experimental data.

引用

页码：13028 / 13036

页数：9

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