| Ab initio study of the transition-metal carbene cations |
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| 引用本文： | 李吉海,冯大诚,冯圣玉. Ab initio study of the transition-metal carbene cations[J]. 中国科学B辑(英文版), 1999, 42(1): 83-88. DOI: 10.1007/BF02883041 |
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| 作者姓名： | 李吉海 冯大诚 冯圣玉 |
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| 作者单位： | Chemical College of Shandong University，Ji'nan 250100，China |
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| 基金项目： | Project supported by the National Natural Science Foundation of China (Grant No. 29170070) |
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| 摘 要： | The geometries and bonding characteristics of the first-row transition-metal carbene cations MCH_2~ were investigated by ab initio molecular orbital theory (HF/LANL2DZ). All of MCH_2~ are coplanar. In the closed shell structures the C bonds to M with double bonds; while in the open shell structures the partial double bonds are formed, because one of the σ and π orbitals is singly occupied. It is mainly the π-type overlap between the 2p_x orbital of C and 4p_x, 3d_(xz), orbitals of M~ that forms the π orbitals. The dissociation energies of C—M bond appear in periodic trend from Sc to Cu. Most of the calculated bond dissociation energies are close to the experimental ones.
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Ab initio study of the transition-metal carbene cations |
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| Jihai Li,Dacheng Feng,Shengyu Feng. Ab initio study of the transition-metal carbene cations[J]. Science in China(Chemistry), 1999, 42(1): 83-88. DOI: 10.1007/BF02883041 |
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| Authors: | Jihai Li Dacheng Feng Shengyu Feng |
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| Affiliation: | 1. Chemical College of Shandong University, 250100, Ji’nan, China
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| Abstract: | The geometries and bonding characteristics of the first-row transition-metal carbene cations MCH 2 + were investigated byab initio molecular orbital theory (HF/LAYL2DZ). All of MCH 2 k are coplanar. In the closed shell structures the C hlnds to M with double bonds:while in the open shell structures the partial double bonds are formed. because one of the σ and π orbitals is singly occupied. It is mainly the π-type overlap between the 2p x orbital of C and 4p x , 3d xx orbitals of M+ that forms the π orbitals. The dissociation energies of C—M bond appear in periodic trend from Sc to Cu. Most of the calculated band dissociation energies are close to the experimental ones. |
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| Keywords: | transition-metal carbene cation geometry molecular orbital bond dissociation energy ab initio calculations. |
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