卡宾CH2及其衍生物参与形成的σ-hole磷键作用的理论研究  

Theoretical Study on theσ-hole Pnicogen Bonds Containing Carbene CH2and Its Derivatives

作　　者：张雪英[1] 林慧 张利利 李文艳 ZHANG Xueying;LIN Hui;ZHANG Lili;LI Wenyan(College of Chemistry and Material Science,Hebei Normal University,Hebei Shijiazhuang 050024,China)

机构地区：[1]河北师范大学化学与材料科学学院,河北石家庄050024

出　　处：《河北师范大学学报（自然科学版）》2020年第4期335-343,共9页Journal of Hebei Normal University：Natural Science

基　　金：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)。

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OPH3…CX2,OPH3…CX(NH2)和OPZ3…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OPZ3对磷键作用的影响.研究结果表明:OPZ3(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OPH3…CX2,OPH3…CX(NH2)和OPZ3…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,OPH3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OPZ3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.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 Mller-plesset perturbation(MP2)methodology.The effects of mono-substituted carbenes CX(NH2),disubstituted carbenes CX2and tri-substituted OPZ3 on the pnicogen bonds were analyzed.The results show thatσ-hole regions exist in OPZ3(Z=H,F,Cl,Br)molecule,and theσ-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：分子间相互作用 σ-hole 磷键 卡宾 

分 类 号：O64[理学—物理化学]