Ab Initio Study of Lithium-Bonded Complexes with Carbene as an Electron Donor

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• 作者：Qingzhong Li ; Haozhen Wang ; Zhenbo Liu ; Wenzuo Li ; Jianbo Cheng ; Baoan Gong ; Jiazhong Sun
• 刊名：Journal of Physical Chemistry A
• 出版年：2009
• 出版时间：December 24, 2009
• 年：2009
• 卷：113
• 期：51
• 页码：14156-14160
• 全文大小：122K
• 年卷期：v.113,no.51(December 24, 2009)
• ISSN：1520-5215

文摘

The complexes H₂C-LiX (X = H, OH, F, Cl, Br, CN, NC, CH₃, C₂H₃, C₂H, NH₂) have been studied with quantum chemical calculations at the MP2/6-311++G(d,p) level. A new type of lithium bond was proposed, in which the carbene acts as the electron donor. This new type of lithium bond was characterized in view of the geometrical, spectral and energetic parameters. The Li—X bond elongates in all lithium bonded complexes. The Li—X stretch vibration has a red shift in the complexes H₂C-LiX (X = H, OH, F); however, it exhibits a blue shift in the complexes H₂C-LiX (X = Cl, Br, CN, NC, CH₃, C₂H₃, C₂H, NH₂). The binding energies are in a range of 16.88−21.13 kcal/mol, indicating that the carbene is a good electron donor in the interaction. The energy decomposition analyses show that the electrostatic contribution is largest, polarization counterpart is followed, and charge transfer is smallest. The effect of substitution and hybridization on this type of lithium bond has also been investigated.