A bioinspired oxoiron(iv) motif supported on a N2S2 macrocyclic ligand

被引：21

作者：

Deutscher, Jennifer ^{[1
]}

Gerschel, Philipp ^{[2
]}

Warm, Katrin ^{[1
]}

Kuhlmann, Uwe ^{[3
]}

Mebs, Stefan ^{[4
]}

Haumann, Michael ^{[4
]}

Dau, Holger ^{[4
]}

Hildebrandt, Peter ^{[3
]}

Apfel, Ulf-Peter ^{[2
,5
]}

Ray, Kallol ^{[1
]}

机构：

[1] Humboldt Univ, Inst Chem, Brook Taylor Str 2, D-12489 Berlin, Germany

[2] Ruhr Univ Bochum, Anorgan Chem 1, Univ Str 150, D-44780 Bochum, Germany

[3] Tech Univ Berlin, Inst Chem, Fak 2 Str 17,Juni 135, D-10623 Berlin, Germany

[4] Free Univ Berlin, Inst Phys, Arnimallee 14, D-14195 Berlin, Germany

[5] Fraunhofer UMSICHT, Dept Electrosynth, Osterfelder Str 3, D-46047 Oberhausen, Germany

来源：

CHEMICAL COMMUNICATIONS | 2021年 / 57卷 / 23期

关键词：

CHLOROPEROXIDASE COMPOUND-II; MONONUCLEAR NONHEME IRON; DIOXYGEN ACTIVATION; OXIDATION REACTIONS; 2-STATE REACTIVITY; CYTOCHROME-P450; SPECTROSCOPY; MECHANISM; OXO;

D O I：

10.1039/d1cc00250c

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A mononuclear oxoiron(iv) complex 1-trans bearing two equatorial sulfur ligations is synthesized and characterized as an active-site model of the elusive sulfur-ligated Fe-IV = O intermediates in non-heme iron oxygenases. The introduction of sulfur ligands weakens the Fe = O bond and enhances the oxidative reactivity of the Fe-IV = O unit with a diminished deuterium kinetic isotope effect, thereby providing a compelling rationale for nature's use of the cis-thiolate ligated oxoiron(iv) motif in key metabolic transformations.

引用

页码：2947 / 2950

页数：4

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