Sn(OTf)2催化活化D-A环丙烷的密度泛函研究张金生;李勇;陈卓;杜海军【期刊名称】《贵州师范大学学报（自然科学版）》【年(卷),期】2007(025)003【摘要】The activation mechanism of Sn(OTf)2-catalyzed Donor-Acceptor (D-A) cyclopropane bearing a malonyl diester accepter group and carbon based resonance donor substituent has been investigated by using density function theory. The geometries for all the stationary points were fully optimized at the B3LYP/6-31G level and the solvent effects were explored by single-point calculations at the B3LYP/6-311G(d,p) level with polarizable continuum model (PCM). The activation mechanism of Sn(OTf)2 catalyzed D-A cyclopropane is suggested to be the increase of σ(C1-C2) bond dipole moment and the decrease of natural bond orbital (NBO) energy of σ*(C1-C2) due to the Sn(II) ion coordination with the D-A cyclopropane, thus the D-A cyclopropane exhibits ambiphilic behavior and σ(C1-C2) is apt to cleavage in the cycloaddition reactions.%用量子化学密度泛函理论对路易斯酸Sn(OTf)2催化活化供电子-吸电子环丙烷的机理进行了量子化学研究. 在B3LYP/6-31G计算水平全优化了反应势能面上所有驻点的几何结构, 用自洽反应场极化连续介质模型分别在B3LYP/6-31G和B3LYP/6-311G(d,p)计算水平计算了单点溶剂化效应. 结果表明, Sn(OTf)2催化活化D-A环丙烷是通过它们的配位作用增大C1-C(2)偶极矩和降低反键轨道σ*(C1-C2)的能量来实现的【总页数】5页(P93-97)【作者】张金生;李勇;陈卓;杜海军【作者单位】贵州师范大学,理学院,贵州,贵阳,550001;贵州民族学院,环境与科学学院,贵州,贵阳,550025;贵州师范大学,理学院,贵州,贵阳,550001;贵州民族学院,环境与科学学院,贵州,贵阳,550025【正文语种】中文【中图分类】O614.12+1【相关文献】1.铜类卡宾催化乙烯环丙烷化反应途径的密度泛函研究 [J], 张兴辉;耿志远;王永成;方冉;王冬梅;戴国梁;吕玲玲;赵存元2.Keggin型多酸负载的单原子催化剂(M1/POM,M=Ni,Pd,Pt,Cu,Ag,Au,POM=[PW12O40]3-)活化氮气分子的密度泛函理论计算研究 [J], 尹玥琪;蒋梦绪;刘春光3.单原子催化剂Ti/Ti3C2O2催化氧化甲醛的密度泛函理论研究 [J], 周君慧;刘冠兰;姜全国;赵伟娜;敖志敏;安太成4.高催化活性M-BHT(M=Co,Cu)电催化还原CO2为CH4的密度泛函理论研究[J], 杨涛;姚会影;李青;郝伟;迟力峰;朱嘉5.亚甲基环丙烷与1,3-双羰基化合物自由基不对称环加成反应的密度泛函研究 [J], 张宝辉;李明;申伟;李英;王司雷因版权原因，仅展示原文概要，查看原文内容请购买。
