Discovery of σ-hole interactions involving ylides

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• 作者：Jiannan Ji (1)
  Yanli Zeng (1)
  Xueying Zhang (1)
  Shijun Zheng (1)
  Lingpeng Meng (1)
  
• 关键词：Electrostatic potential ; Halogen bond ; σ ; hole interaction ; Ylide
• 刊名：Journal of Molecular Modeling
• 出版年：2013
• 出版时间：November 2013
• 年：2013
• 卷：19
• 期：11
• 页码：4887-4895
• 全文大小：
• 作者单位：Jiannan Ji (1)
  Yanli Zeng (1)
  Xueying Zhang (1)
  Shijun Zheng (1)
  Lingpeng Meng (1)
  
  1. College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang, 050024, China
  
• ISSN：0948-5023

文摘

The positive electrostatic potentials (σ-hole) have been found in ylides CH2XH3 (X = P, As, Sb) and CH2YH2 (Y = S, Se, Te), on the outer surfaces of group VA and VIA atoms, approximately along the extensions of the C–X and C–Y bonds, respectively. These electrostatic potentials suggest that the above ylides can interact with nucleophiles to form weak, directional noncovalent interactions similar to halogen bonding interactions. MP2 calculations have confirmed the formation of CH2XH3···HM complexes (X = P, As, Sb; M = BeH, ZnH, MgH, Li, Na). The interaction energies, interaction distances, topological properties (electron density and its Laplacian), and energy properties (kinetic electron energy density and potential electron energy density) at the X(1)···H(10) bond critical points are all correlated with the most negative electrostatic potential value of HM, indicating that electrostatic interactions play an important role in these weak X···H interactions. Similar to the halogen bonding interactions, weak interactions involving ylides may be significant in several areas such as organic synthesis, crystal engineering, and design of new materials.