Substituent effects on the imine derivatives:A theoretical research from quantum chemistry computation and correlation analysis
作者单位：Department of Biology and ChemistryCity University of Hong KongKowloonHong gong
会议名称：《第九届全国计算（机）化学学术会议》
会议日期：2007年
学科分类：07[理学] 070304[理学-物理化学(含∶化学物理)] 0703[理学-化学]
关 键 词：Substituent effects Imine derivatives Quantumn chemistry computation Correlation analysis
摘 要：The substituent(R=F,OH,OCF3,OCH3,CN,CHO,NH2,NO,CH3,CF3, PH2,SH,SiH3)effects on methanimine(CH2=NH)were investigated using B3LYP and G3 calculations,together with correlation analysis.The results indicate that the charge variation on the C=N bond atoms can be characterized by resonance constants and electronegativities of substituent groups.The FCP(Fractional bond Critical Point) derived from AIM(Atoms in molecules)computation displays a good correlation with the group electronegativity and the AIM charge.The isodesmic reaction study suggests that the electropositive groups would stabilize the N-substituted imines while the highly electronegative substituents along with strong p-donating character would obviously stabilize C-substituted imine derivatives.On the basis of NBO(Nature Bond Orbital)results,the variation of the trans/cis inversion barriers can be attributed to the hyperconjugation of the inverting nitrogen lone pair into the adjacent s(C-R) orbital in the transition state and displays strong dependence upon the electronegativity of substituent groups.