| 过渡金属铁配合物Fe(CO)5-x(PR3)x的结构与性质的理论研究 |
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| 引用本文： | 郭彩红,李海宇,李俊,贾建峰,武海顺.过渡金属铁配合物Fe(CO)5-x(PR3)x的结构与性质的理论研究[J].无机化学学报,2013,29(18). |
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| 作者姓名： | 郭彩红 李海宇 李俊 贾建峰 武海顺 |
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| 作者单位： | 磁性分子与磁信息材料教育部重点实验室, 山西师范大学化学与材料科学学院, 临汾 041004,磁性分子与磁信息材料教育部重点实验室, 山西师范大学化学与材料科学学院, 临汾 041004,磁性分子与磁信息材料教育部重点实验室, 山西师范大学化学与材料科学学院, 临汾 041004,磁性分子与磁信息材料教育部重点实验室, 山西师范大学化学与材料科学学院, 临汾 041004,磁性分子与磁信息材料教育部重点实验室, 山西师范大学化学与材料科学学院, 临汾 041004 |
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| 基金项目： | 国家自然科学基金（No.21203115，21373131，21571119）资助项目。 |
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| 摘 要： | 采用密度泛函理论（DFT）对一系列低价铁化合物Fe（CO）5-x（PR3）x（x=1~3，R=H，F，Me）的几何结构、电子结构、成键特点以及热力学性质进行了理论研究。结果表明引入膦配体后不会造成Fe（CO）x（PR3）5-x的几何结构畸变，为略扭曲的三角双锥形。自然键轨道（NBO）分析显示，膦配体与羰基铁基团间存在电荷转移，有效增强Fe-CO之间的共价作用。多数稳定结构Fe（CO）x（PR3）5-x的第一膦配体解离能要比第一羰基解离能低，预示Fe（CO）5-x（PR3）x的反应活性比Fe（CO）5有明显提高。
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| 关 键 词： | 密度泛函理论 羰基铁衍生物 膦配体 解离能 自然键轨道(NBO)分析 |
| 收稿时间： | 2016/12/31 0:00:00 |
| 修稿时间： | 2017/5/9 0:00:00 |
Theoretical Study on Structure and Property of Iron Carbonyl Derivatives Fe(CO)5-x(PR3)x |
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| GUO Cai-Hong,LI Hai-Yu,LI Jun,JIA Jian-Feng and WU Hai-Shun.Theoretical Study on Structure and Property of Iron Carbonyl Derivatives Fe(CO)5-x(PR3)x[J].Chinese Journal of Inorganic Chemistry,2013,29(18). |
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| Authors: | GUO Cai-Hong LI Hai-Yu LI Jun JIA Jian-Feng and WU Hai-Shun |
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| Institution: | School of Chemical and Material Science, Shanxi Normal University, Key Laboratory of Magnetic Molecules & Magnetic Information Materials Ministry of Education, Linfen, China, 041004,School of Chemical and Material Science, Shanxi Normal University, Key Laboratory of Magnetic Molecules & Magnetic Information Materials Ministry of Education, Linfen, China, 041004,School of Chemical and Material Science, Shanxi Normal University, Key Laboratory of Magnetic Molecules & Magnetic Information Materials Ministry of Education, Linfen, China, 041004,School of Chemical and Material Science, Shanxi Normal University, Key Laboratory of Magnetic Molecules & Magnetic Information Materials Ministry of Education, Linfen, China, 041004 and School of Chemical and Material Science, Shanxi Normal University, Key Laboratory of Magnetic Molecules & Magnetic Information Materials Ministry of Education, Linfen, China, 041004 |
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| Abstract: | The geometric structures, electronic configurations, bonding characteristic, and thermodynamic properties of low valence iron complexes Fe(CO)5-x(PR3)x (x=1~3, R=H, F, Me) were studied using the density functional theory (DFT) method. The results show that the geometric framework of Fe(CO)5-x(PR3)x is not aberrant but maintain the distorted trigonal bipyramidal structure after the introduction of phosphorus ligand(s). Natural bond orbital (NBO) analysis show that there is charge transfer between the phosphorus ligand (s) to the carbonyl iron fragment. Moreover, the covalent interaction between Fe and CO was is enhanced. The phosphorus ligand dissociation energy is lower than the first carbonyl dissociation energy from the most stable structure Fe(CO)5-x(PR3)x. This indicates that the reactivity of Fe(CO)5-x(PR3)x is largely greater than Fe(CO)5. |
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| Keywords: | density functional theory iron carbonyl derivatives phosphorus ligand dissociation energy natural bond orbital (NBO) analysis |
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