Theoretical study of the effect of ligand topology on Fe(IV)O and Ru(IV)O complex reactivities
文献类型：期刊论文
| 作者 | Tang, Zhe1; Wang, Yi1; Cui, Xiaolei1; Yang, Ying1; Tian, Jing1; Fei, Xu1; Lv, Shuangjiang2 |
| 刊名 | INORGANICA CHIMICA ACTA
 |
| 出版日期 | 2016-03-24 |
| 卷号 | 443页码:235-242 |
| 关键词 | Non-heme Density Functional Theory Calculation Hydrogen Abstraction Ligand Topology Effect |
| ISSN号 | 0020-1693 |
| DOI | 10.1016/j.ica.2016.01.004 |
| 文献子类 | Article |
| 英文摘要 | Density functional theory calculations were carried out to clarify the effect of ligand topology on the stability and reactivity of cis-alpha-[Fe-IV(O)(BQCN)](2+) (Fe-2a), cis-beta-[Fe-IV(O)(BQCN)](2+) (Fe-2b), cis-alpha-[Ru-IV(O) (BQCN)](2+) (Ru-2a) and cis-beta-[Ru-IV(O)(BQCN)](2+) (Ru-2b) (BQCN = N,N'-dimethyl-N,N'-bis(8-quinolyl)-cyclohexanediamine). All the iron and ruthenium isomers possess the triplet ground states. The relative stability between the two iron isomers follows the order of Fe-2a > Fe-2b, which is in agreement with the conclusions of Hong et al. Moreover, the trend of the relative stability of the two ruthenium isomers is Ru-2a > Ru-2b. The Density-of-States spectrums represent that the contribution of BQCN ligand to Fe-3-2b is more than the corresponding contribution to Fe-3-2a. The iron isomers react with isopropylbenzene via a two-state reactivity pattern on competing triplet and quintet spin states, while the ruthenium isomers react with isopropylbenzene by a single-state mechanism, only on the triplet spin state. The H-abstraction is affected by the tunneling contribution, which can decrease the reaction barriers. By adding the ZPE correction, PCM model assessed by DFT-D3 (BJ) and the tunneling correction, the analysis of the trend of the hydrogen-abstraction reactions barriers shows that Fe-2a is the more reactive than Fe-2b with the higher Fe-IV/III redox potential. Moreover, for the ruthenium complexes, although Ru-2a is the more reactive than Ru-2b, only 0.6 kcal/mol lower. Above all, the ligand topology has little effect on the reactivities of the [Ru-IV(O)(BQCN)](2+) complexes. (C) 2016 Elsevier B.V. All rights reserved. |
| WOS关键词 | NONHEME FE-IV=O ; DENSITY-FUNCTIONAL THERMOCHEMISTRY ; H BOND ACTIVATION ; GAUSSIAN-BASIS SETS ; IRON ACTIVE-SITES ; ELECTRONIC-STRUCTURES ; 2-STATE REACTIVITY ; AB-INITIO ; IRON(IV)-OXO COMPLEXES ; DIOXYGEN ACTIVATION |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:000369070900031 |
| 出版者 | ELSEVIER SCIENCE SA |
| 源URL | [http://cas-ir.dicp.ac.cn/handle/321008/171336]  |
| 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 |
| 通讯作者 | Wang, Yi; Lv, Shuangjiang |
| 作者单位 | 1.Dalian Polytech Univ, Sch Biol Engn, Dalian 116034, Peoples R China 2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China |
| 推荐引用方式 GB/T 7714 | Tang, Zhe,Wang, Yi,Cui, Xiaolei,et al. Theoretical study of the effect of ligand topology on Fe(IV)O and Ru(IV)O complex reactivities[J]. INORGANICA CHIMICA ACTA,2016,443:235-242. |
| APA | Tang, Zhe.,Wang, Yi.,Cui, Xiaolei.,Yang, Ying.,Tian, Jing.,...&Lv, Shuangjiang.(2016).Theoretical study of the effect of ligand topology on Fe(IV)O and Ru(IV)O complex reactivities.INORGANICA CHIMICA ACTA,443,235-242. |
| MLA | Tang, Zhe,et al."Theoretical study of the effect of ligand topology on Fe(IV)O and Ru(IV)O complex reactivities".INORGANICA CHIMICA ACTA 443(2016):235-242. |
入库方式： OAI收割
来源：大连化学物理研究所
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