高等学校化学学报2012，Vol.33Issue(8)：1799-1803,5.DOI:10.3969/j.issn.0251-0790.2012.08.030
基于非血红素铁模型配合物[FeⅣ(O)(N4Py)]2+的新型N杂环卡宾配合物的理论设计
Theoretical Design of a New N-Heterocyclic Carbene Complex Based on Non-heme Iron Complex [Fe Ⅳ (O) (N4Py)] 2+
摘要
Abstract
Based on non-heme iron complex [FeⅣ(O) (N4Py) ]2+[N4Py = N,N-bis(2-pyridylmethyl)-N-bis (2-pyridylmethylamine) ] , a new designed iron-carbene complex [FeIV(O) (NHC)4]2+ was theoretically designed. The geometric and electronic structures of [ FeⅣ(0)·(NHC)4]2+ were studied via density functional theory and B3LYP method, and the [ FeⅣ(0) (NHC)4]2+catalytic properties versus cyclohexane were investigated. The calculation results show that the energy of the quintet spin state of [FeⅣCO) (NHC)4]2+ is ca. 4. 8 kJ/mol higher than that of the triplet ground state, suggesting that the quintet spin state can hardly participate in the reaction. The N-heterocyclic carbene (NHC) equatorial ligand was found to have stronger cr-dona-ting and greater steric hindrance than N4Py ligand, indicating that the complex [FeⅣ(O)(NHC)4]2+ is more stable than [ FeⅣ(0) ( N4Py)]2+ complex. Moreover, on the triplet spin surface, the energy barrier of [FeIV(O)(NHC)4]2+ has higher activation energy than that of [Few(0) (N4Py) ]2+ by 2.0 kj/mol via a single-state reactivity pattern, implying that [ FeⅣ(0) (N4Py)]24 complex is more reactive than [FeIV(O)(NHC)4]2t complex.关键词
非血红素/N杂环卡宾/密度泛函理论/轨道系数/反应机理Key words
Non-heme/ N-Heterocyclic carbene/ Density functional theory/ Orbital coefficient/ Reaction mechanism分类
化学化工引用本文复制引用
王一,张鹏,杨鲲,侯英敏..基于非血红素铁模型配合物[FeⅣ(O)(N4Py)]2+的新型N杂环卡宾配合物的理论设计[J].高等学校化学学报,2012,33(8):1799-1803,5.基金项目
国家自然科学基金(批准号:11047110)资助. （批准号:11047110）
