Discovery of sigma-hole interactions involving ylides

作者：Ji Jiannan; Zeng Yanli^*; Zhang Xueying; Zheng Shijun; Meng Lingpeng

来源：Journal of Molecular Modeling, 2013, 19(11): 4887-4895.

DOI：10.1007/s00894-013-1992-8

• Electrostatic potential
• Halogen bond
• sigma-hole interaction
• Ylide

The positive electrostatic potentials (sigma-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 center dot center dot center dot 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)center dot center dot center dot 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 center dot center dot center dot 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.

• 出版日期2013-11
• 单位河北师范大学