| 乙烯、乙炔和苯与氨基锂间的π型锂键相互作用 |
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| 引用本文： | 袁,焜,刘艳芝,吕玲玲,朱元成,张,继,张俊彦.乙烯、乙炔和苯与氨基锂间的π型锂键相互作用[J].中国化学,2009,27(4):697-702. |
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| 作者姓名： | 袁 焜 刘艳芝 吕玲玲 朱元成 张 继 张俊彦 |
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| 作者单位： | 1天水师范学院 生命科学与化学学院，天水 741000 ;2西北师范大学 生命科学学院，兰州 730070 ;3 中国科学院 兰州物理研究所，兰州 730000 ; |
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| 摘 要： | 分别在DFT-B3LYP和MP2/6-311++G**水平上求得乙烯、乙炔和苯与氨基锂锂键复合物势能面上的3个几何构型. 频率分析表明，3个构型均为稳定构型. 计算结果表明，形成锂键复合物后，质子供体N(2)- Li(4)的键长明显增大，且其伸缩振动的频率发生了不同程度的红移. 分别在乙烯…氨基锂、乙炔…氨基锂和苯…氨基锂三种复合物中，经MP2/6-311++G**水平计算的同时含基组重叠误差(BSSE)和零点振动能校正的单体间锂键相互作用能分别为-26.04、-24.86 和 -30.02 kJ·mol-1. 自然键轨道理论（NBO）分析表明单体间的弱相互作用属于π-s型锂键.
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| 关 键 词： | π型锂键 氨基锂 理论计算 自然键轨道理论 |
| 收稿时间： | 2008-8-12 |
| 修稿时间： | 2008-10-21 |
π Type Lithium Bond Interaction between Ethylene,Acetylene, or Benzene and Amido‐lithium |
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| Kun YUAN,Yanzhi LIU,Lingling Lü,Yuancheng ZHU,Ji ZHANG,Junyan ZHANG.π Type Lithium Bond Interaction between Ethylene,Acetylene, or Benzene and Amido‐lithium[J].Chinese Journal of Chemistry,2009,27(4):697-702. |
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| Authors: | Kun YUAN Yanzhi LIU Lingling LÜ Yuancheng ZHU Ji ZHANG Junyan ZHANG |
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| Institution: | 1. College of Life‐science and Chemistry, Tianshui Normal University, Tianshui, Gansu 741001, China;2. College of Life Science, Northwest Normal University, Lanzhou, Gansu 730070, China;3. State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, Gansu 730000, China |
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| Abstract: | The optimization geometries and interaction energy corrected by basis set super‐position error (BSSE) of the lithium bond complexes between ethylene, acetylene, or benzene and amido‐lithium have been calculated at the B3LYP/6‐311++G???? and MP2/6‐311++G???? levels. And only one configuration was obtained for each lithium bond system. All the equilibrium geometries were confirmed to be stable state by analytical frequency computations. The calculations showed that all the N(2)–Li(4) bond lengths increased obviously and the red shift of N(2)–Li(4) stretching frequency occurred after complexes formed. The calculated binding energies with BSSE and zero‐point vibrational energy corrections of complexes I , II and III are ?26.04, ?24.86 and ?30.02 kJ·mol?1 via an MP2 method, respectively. Natural bond orbital (NBO) theory analysis revealed that the three complexes were all formed with π type lithium bond interaction between ethylene, acetylene, or benzene and amido‐lithium. |
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| Keywords: | π‐type lithium bond NH2Li theoretical calculation NBO |
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