Steric hindrance effect of the equatorial ligand on Fe(IV)O and Ru(IV)O complexes: a density functional study
文献类型：期刊论文
| 作者 | Wang, Yi1,2; Han, Keli1 |
| 刊名 | journal of biological inorganic chemistry
 |
| 出版日期 | 2010-03-01 |
| 卷号 | 15期号:3页码:351-359 |
| 关键词 | Non-heme Hydrogen abstraction Isomer Density functional theory |
| 产权排序 | 1;1 |
| 通讯作者 | 韩克利 |
| 英文摘要 | the geometric structures and mechanisms for hydrogen abstraction from cyclohexane for four high-valent complexes, [fe(iv)(o)(tmc)(ncme)](2+) (where tmc is 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; 1-ncme), the inverted isomer [fe(iv)(ncme)(tmc)(o)](2+) (2-ncme), [ru(iv)(o)(tmc)(ncme)](2+) (the ruthenium analogue of 1-ncme; 3-ncme), and the inverted isomer [ru(iv)(ncme)(tmc)(o)](2)+ (4-ncme), were investigated using density functional theory. the axial ncme ligand was found to be sterically more hindered in 2-ncme than in 1-ncme, which is in accord with the calculated results that the fe-l(axial) distance is longer in the former. both 1-ncme and 2-ncme are capable of hydrogen abstraction from cyclohexane via two-state reactivity patterns. in contrast, 3-ncme and 4-ncme react with cyclohexane by a single-state mechanism. the reaction pathways computed reveal that 2-ncme is more reactive than 1-ncme, in agreement with experimental results, whereas the reactivity of 3-ncme and 4-ncme shows little dependence on whether the oxo unit is syn or anti to the four n-methyl groups. our analysis shows that along the reaction pathway for 2-ncme in the triplet spin state, the ncme ligand moves away from the iron center, and therefore the energy of the sigma(z)*(2) (alpha-spin) orbital decreases and an electron is transferred to this orbital. finally, we calculated the kinetic isotope effect and investigated the relationship between this effect and reaction barriers. |
| WOS标题词 | science & technology ; life sciences & biomedicine ; physical sciences |
| 类目[WOS] | biochemistry & molecular biology ; chemistry, inorganic & nuclear |
| 研究领域[WOS] | biochemistry & molecular biology ; chemistry |
| 关键词[WOS] | nonheme fe-iv=o ; iron active-sites ; c-h hydroxylation ; electronic-structures ; 2-state reactivity ; dioxygen activation ; ruthenium porphyrin ; spectroscopic characterization ; iron(iv)-oxo complexes ; oxoiron(iv) complexes |
| 收录类别 | SCI |
| 原文出处 | false |
| 语种 | 英语 |
| WOS记录号 | WOS:000275104400006 |
| 公开日期 | 2010-11-30 |
| 源URL | [http://159.226.238.44/handle/321008/103043]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 作者单位 | 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China 2.Chinese Acad Sci, Grad Sch, Beijing 100039, Peoples R China |
| 推荐引用方式 GB/T 7714 | Wang, Yi,Han, Keli. Steric hindrance effect of the equatorial ligand on Fe(IV)O and Ru(IV)O complexes: a density functional study[J]. journal of biological inorganic chemistry,2010,15(3):351-359. |
| APA | Wang, Yi,&Han, Keli.(2010).Steric hindrance effect of the equatorial ligand on Fe(IV)O and Ru(IV)O complexes: a density functional study.journal of biological inorganic chemistry,15(3),351-359. |
| MLA | Wang, Yi,et al."Steric hindrance effect of the equatorial ligand on Fe(IV)O and Ru(IV)O complexes: a density functional study".journal of biological inorganic chemistry 15.3(2010):351-359. |
入库方式： OAI收割
来源：大连化学物理研究所
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