Heterolytic O-O Bond Cleavage Upon Single Electron Transfer to a Nonheme Fe(III)-OOH Complex

被引：5

作者：

Bohn, Antoine ^{[1
]}

Senechal-David, Katell ^{[1
]}

Rebilly, Jean-Noel ^{[1
]}

Herrero, Christian ^{[1
]}

Leibl, Winfried ^{[2
]}

Anxolabehere-Mallart, Elodie ^{[3
]}

Banse, Frederic ^{[1
]}

机构：

[1] Univ Paris Saclay, CNRS, Inst Chim Mol & Mat Orsay, F-91405 Orsay, France

[2] Univ Paris Saclay, CEA, CNRS, Inst Integrat Biol Cell I2BC, F-91198 Gif Sur Yvette, France

[3] Univ Paris Cite, CNRS, Lab Electrochim Mol, F-75013 Paris, France

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2022年 / 28卷 / 53期

关键词：

OLEFIN CIS-DIHYDROXYLATION; IRON CATALYSTS; OXIDATIVE DECARBOXYLATION; DIOXYGEN ACTIVATION; ACTIVE-SITES; C-H; FE; INTERMEDIATE; REACTIVITY; CATALASE;

D O I：

10.1002/chem.202201600

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The one-electron reduction of the nonheme iron(III)-hydroperoxo complex, [Fe-III(OOH)(L-5(2))](2+) (L-5(2)=N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine), carried out at -70 degrees C results in the release of dioxygen and in the formation of [Fe-II(OH)(L-5(2))](+) following a bimolecular process. This reaction can be performed either with cobaltocene as chemical reductant, or electrochemically. These experimental observations are consistent with the disproportionation of the hydroperoxo group in the putative Fe-II(OOH) intermediate generated upon reduction of the Fe-III(OOH) starting complex. One plausible mechanistic scenario is that this disproportionation reaction follows an O-O heterolytic cleavage pathway via a Fe-IV-oxo species.

引用

页数：6

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