在线阅读 --自然科学版 2020年4期《卡宾CH2及其衍生物参与形成的σ hole磷键作用的理论研究》
卡宾CH2及其衍生物参与形成的σ hole磷键作用的理论研究--[在线阅读]
张雪英, 林慧, 张利利, 李文艳
河北师范大学 化学与材料科学学院, 河北 石家庄 050024
起止页码: 335--343页
DOI: 10.13763/j.cnki.jhebnu.nse.2020.04.009
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.

Theoretical Study on the σ-hole Pnicogen Bonds Containing Carbene CH2 and Its Derivatives
ZHANG Xueying, LIN Hui, ZHANG Lili, LI Wenyan
College of Chemistry and Material Science, Hebei Normal University, Hebei Shijiazhuang 050024, China
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.

收稿日期: 2019-12-20
基金项目: 河北省自然科学基金(2018205198);河北师范大学重点项目(L2018Z04);河北师范大学大学生创新创业训练计划项目(201810094004)

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