Mechanistic insights into the biomimetic catalytic hydroxylation of arenes by a molecular Fe(NHC) complex

被引：11

作者：

Lindhorst, Anja C. ^{[1
,2
]}

Drees, Markus ^{[2
,3
]}

Bonrath, Werner ^{[4
]}

Schuetz, Jan ^{[4
]}

Netscher, Thomas ^{[4
]}

Kuehn, Fritz E. ^{[1
,2
]}

机构：

[1] Tech Univ Munich, Dept Chem, Mol Catalysis, Lichtenbergstr 4, D-85747 Garching, Germany

[2] Tech Univ Munich, Catalysis Res Ctr, Lichtenbergstr 4, D-85747 Garching, Germany

[3] Tech Univ Munich, Dept Chem, Chair Inorgan & Met Organ Chem, Lichtenbergstr 4, D-85747 Garching, Germany

[4] DSM Nutr Prod, Res & Dev, POB 2676, CH-4002 Basel, Switzerland

来源：

JOURNAL OF CATALYSIS | 2017年 / 352卷

关键词：

Iron; N-heterocyclic carbene; Hydroxylation; Arene oxidation; Reaction mechanism; Isotope effect; NIH shift; Density functional theory calculations; NONHEME IRON CENTER; C-H BONDS; AROMATIC HYDROXYLATION; BASIS-SETS; NIH SHIFT; IRON(IV)-OXO COMPLEXES; OXYGENATION REACTIONS; ORBITAL METHODS; DENSITY; OXIDATION;

D O I：

10.1016/j.jcat.2017.06.018

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：

The mechanism of the hydroxylation of benzene by an iron(II) bis(NHC) complex, [Fe-II(NCCN)(CH3CN)(2)] (PF6)(2) (1; NCCN = bis(o-imidazol-2-ylidenepyridine)methane), in the presence of hydrogen peroxide was investigated. The invariance of the catalytic system towards the presence of radical scavengers and an inverse intermolecular kinetic isotope effect (ICIE) allow to rule out a hydrogen abstraction pathway. Additionally, using 1,3,5-[D-3]benzene as substrate, NIH-shift products were detected, resembling the reactivity of naturally occurring enzymes and some molecular biomimetic iron complexes. Supported by density functional theory calculations, the aromatic hydroxylation reaction is proposed to proceed via an iron-arene sigma-complex as intermediate species. (C) 2017 Elsevier Inc. All rights reserved.

引用

页码：599 / 605

页数：7

共 45 条

[1] μ-Nitrido Diiron Macrocyclic Platform: Particular Structure for Particular Catalysis [J].

Afanasiev, Pavel ;

Sorokin, Alexander B. .

ACCOUNTS OF CHEMICAL RESEARCH, 2016, 49 (04) :583-593

[2] Keto-enol tautomerism in linear and cyclic β-diketones:: A DFT study in vacuo and in solution [J].

Alagona, Giuliano ;

Ghio, Caterina .

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 2008, 108 (10) :1840-1855

[3] Transition-Metal-Catalyzed Synthesis of Hydroxylated Arenes [J].

Alonso, Diego A. ;

Najera, Carmen ;

Pastor, Isidro M. ;

Yus, Miguel .

CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (18) :5274-5284

[4]

[Anonymous], 2015, GAUSSIAN 09 REVISION

[5] DENSITY-FUNCTIONAL STUDY OF INTRINSIC AND ENVIRONMENTAL-EFFECTS IN THE TAUTOMERIC EQUILIBRIUM OF 2-PYRIDONE [J].

BARONE, V ;

ADAMO, C .

JOURNAL OF PHYSICAL CHEMISTRY, 1995, 99 (41) :15062-15068

[6] Mechanism of aromatic hydroxylation by an activated feIV=O core in tetrahydrobiopterin-dependent hydroxylases [J].

Bassan, A ;

Blomberg, MRA ;

Siegbahn, PEM .

CHEMISTRY-A EUROPEAN JOURNAL, 2003, 9 (17) :4055-4067

[7] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[8] EFFICIENT DIFFUSE FUNCTION-AUGMENTED BASIS SETS FOR ANION CALCULATIONS. III. THE 3-21+G BASIS SET FOR FIRST-ROW ELEMENTS, LI-F [J].

CLARK, T ;

CHANDRASEKHAR, J ;

SPITZNAGEL, GW ;

SCHLEYER, PV .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 1983, 4 (03) :294-301

[9] Biomimetic nonheme iron catalysts for alkane hydroxylation [J].

Costas, M ;

Chen, K ;

Que, L .

COORDINATION CHEMISTRY REVIEWS, 2000, 200 :517-544

[10] Combined experimental and theoretical study on aromatic hydroxylation by mononuclear nonheme iron(IV)-oxo complexes [J].

de Visser, Sam P. ;

Oh, Kyungeun ;

Han, Ah-Rim ;

Nam, Wonwoo .

INORGANIC CHEMISTRY, 2007, 46 (11) :4632-4641

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