Theoretical studies on the reaction mechanism of alcohol oxidation by high-valent iron-oxo complex of non-heme ligand

被引：7

作者：

Cheng, Lin ^{[1
,3
]}

Wang, Jinping ^{[2
]}

Wang, Meiyan ^{[1
,3
]}

Wu, Zhijian ^{[1
]}

机构：

[1] Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Rare Earth Resource Utilizat, Changchun 130022, Peoples R China

[2] Qingdao Agr Univ, Dept Appl Chem, Qingdao 266109, Peoples R China

[3] Chinese Acad Sci, Grad Sch, Beijing 100049, Peoples R China

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2010年 / 12卷 / 16期

基金：

中国国家自然科学基金;

关键词：

C-H HYDROXYLATION; PROTON-ABSTRACTION MECHANISM; TRANSITION-METAL-COMPLEXES; GALACTOSE-OXIDASE; AEROBIC OXIDATION; ELECTRONIC-STRUCTURE; 2-STATE REACTIVITY; SPECTROSCOPIC CHARACTERIZATION; COPPER(II) COMPLEXES; ALKANE HYDROXYLATION;

D O I：

10.1039/b917906b

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 catalytic mechanism for the oxidation of methanol to formaldehyde and water catalyzed by the biomimetic non-heme iron complex, [(tpa)(FeO)-O-IV](2+) (tpa = tris(2-pyridylmethyl)amine), is presented by the density functional method B3LYP. Experimentally, acetate and CH3CN could be coordinated to the Fe center as the sixth ligand to form the catalyst [(tpa)Fe(IV)QO](2+). To investigate the detailed reaction mechanisms for the two possible ligands, two models (acetate-bound ferryl model A and CH3CN-bound ferryl model B) are chosen. In total, six routes have been presented for two models. Our calculations show that both acetate and CH3CN could provide reasonable pathways. The calculated energy barriers for these routes are between 19.0 and 23.7 kcal mol(-1) in solution, within the error limits of B3LYP. It is also found that the CH3CN molecule acts only as a ligand throughout the reaction cycle. By contrast, the acetate ligand acts as a proton sink to assist the product formation. In addition, the less polarized solvent is more suitable for the alcohol oxidation catalyzed by non-heme model complexes.

引用

页码：4092 / 4103

页数：12