期刊信息

  • 刊名： 河北师范大学学报（自然科学版）Journal of Hebei Normal University (Natural Science)
  • 主办： 河北师范大学
  • ISSN： 1000-5854
  • CN： 13-1061/N
  • 中国科技核心期刊
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卡宾CH2及其衍生物参与形成的σ hole磷键作用的理论研究

  • 河北师范大学 化学与材料科学学院, 河北 石家庄 050024
  • DOI： 10.13763/j.cnki.jhebnu.nse.2020.04.009

Theoretical Study on the σ-hole Pnicogen Bonds Containing Carbene CH2 and Its Derivatives

摘要/Abstract

摘要：

使用量子化学二阶微扰理论MP2方法，在aug-cc-pVDZ基组水平上研究了卡宾及其衍生物参与形成的磷键O=PH3…CX2，O=PH3…CX（NH2）和O=PZ3…CMe2（X=H，F，Cl，Br，OH，OMe，Me，NMe2，NH2；Z=F，Cl，Br）的结构与性质，分析了单取代卡宾CX（NH2）、双取代卡宾CX2以及三取代O=PZ3对磷键作用的影响.研究结果表明：O=PZ3（Z=H，F，Cl，Br）分子中存在σ-hole区域，可与卡宾作用形成σ-hole磷键；不同取代基对磷键作用的强度具有一定影响，但没有改变磷键作用的性质；复合物O=PH3…CX2，O=PH3…CX（NH2）和O=PZ3…CMe2中磷键作用的强度较弱，分子间作用具有明显的非共价相互作用的特征.能量分解分析表明，O=PH3与卡宾CX2及CX（NH2）之间的磷键作用均以静电作用为主，而对于O=PZ3与CMe2间的磷键作用，随着H被F，Cl，Br取代，分子间作用的主要成分由静电能逐渐转为色散能.

Abstract：

The structures and properties of pnicogen bonds in complexes O=PH3…CX2,O=PH3…CX (NH2),and O=PZ3…CMe2 (X=H,F,Cl,Br,OH,OMe,Me,NMe2,NH2; Z=F,Cl,Br) were studied by means of the Møller-plesset perturbation(MP2) methodology.The effects of mono-substituted carbenes CX(NH2),di-substituted carbenes CX2 and tri-substituted O=PZ3 on the pnicogen bonds were analyzed.The results show that σ-hole regions exist in O=PZ3 (Z=H,F,Cl,Br) molecule,and the σ-hole pnicogen bonds can form with carbenes.Different substituents have a certain effect on the strength,but have little influence on the nature of these pnicogen bonds.The pnicogen bonds between O=PZ3 and carbenes CX2/CX(NH2) are weak and have the characteristics of noncovalent interaction.The intermolecular interactions in the complexes O=PH3…CX2,O=PH3…CX(NH2) are mainly electrostatic interactions.As for complexes O=PZ3…CMe2， the intermolecular interaction is gradually dominated from electrostatic to dispersion force as H atom is replaced by F,Cl,and Br.

关键词

关键词： 分子间相互作用 ; σ-hole ; 磷键 ; 卡宾
Key words： intermolecular interaction ; σ-hole ; pnicogen bond ; carbene

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