Theoretical studies on the reaction mechanism of alcohol oxidation by high-valent iron-oxo complex of non-heme ligand
文献类型：期刊论文
| 作者 | Cheng L ; Wang JP ; Wang MY ; Wu ZJ |
| 刊名 | physical chemistry chemical physics
 |
| 出版日期 | 2010 |
| 卷号 | 12期号:16页码:4092-4103 |
| 关键词 | C-H HYDROXYLATION CATALYZED INTRAMOLECULAR ARYLATION PROTON-ABSTRACTION MECHANISM TRANSITION-METAL-COMPLEXES OXIDASE MODEL COMPLEXES ENERGY CROSSING POINTS GALACTOSE-OXIDASE AEROBIC OXIDATION CYTOCHROME-P450 ENZYMES ELECTRONIC-STRUCTURE |
| ISSN号 | 1463-9076 |
| 通讯作者 | wu zj |
| 中文摘要 | 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. |
| 收录类别 | SCI收录期刊论文 |
| 语种 | 英语 |
| WOS记录号 | WOS:000276469600016 |
| 公开日期 | 2012-06-06 |
| 源URL | [http://ir.ciac.jl.cn/handle/322003/43799]  |
| 专题 | 长春应用化学研究所_长春应用化学研究所知识产出_期刊论文 |
| 推荐引用方式 GB/T 7714 | Cheng L,Wang JP,Wang MY,et al. Theoretical studies on the reaction mechanism of alcohol oxidation by high-valent iron-oxo complex of non-heme ligand[J]. physical chemistry chemical physics,2010,12(16):4092-4103. |
| APA | Cheng L,Wang JP,Wang MY,&Wu ZJ.(2010).Theoretical studies on the reaction mechanism of alcohol oxidation by high-valent iron-oxo complex of non-heme ligand.physical chemistry chemical physics,12(16),4092-4103. |
| MLA | Cheng L,et al."Theoretical studies on the reaction mechanism of alcohol oxidation by high-valent iron-oxo complex of non-heme ligand".physical chemistry chemical physics 12.16(2010):4092-4103. |
入库方式： OAI收割
来源：长春应用化学研究所
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