Comparative Cumulene Substituent Effects: Ketenes, Allenes, Diazomethanes, Diazirines, and Cyclopropenes by ab Initio Molecular Orbital Calculations
Comparative Cumulene Substituent Effects: Ketenes, Allenes, Diazomethanes, Diazirines, and Cyclopropenes by ab Initio Molecular Orbital Calculations
复制标题
比较积烯取代基效应：通过从头算分子轨道计算乙烯酮、丙二烯、重氮甲烷、二氮丙啶和环丙烯
DOI：
10.1021/jo00095a028
复制
发表时间：
1994
影响因子：
3.6
通讯作者：
T. Tidwell
中科院分区：
文献类型：
--
作者：
M. McAllister;T. Tidwell
用从头算方法计算了取代基对烯酮（1）、重氮甲烷（3）、双氮杂环丙烯（4）、联烯（5）和环丙烯（6）的结构和能量的影响，结果表明，1、3和5的等键取代基稳定化能与基团电负性相关，斜率分别为-15.1、-10.6和-1.8。在HF/6- 31 G * +ZPVE/HF/6- 31 G * 水平上，对应于累积多烯的极性依次降低。异构化能为3 ~ 4表明，取代重氮甲烷和双吖丙啶的相对稳定性主要受正电性取代基稳定重氮甲烷的影响
Ab initio calculations of the effect of substituents on the structures and energies of ketenes (1), diazomethanes (3), diazirines (4), allenes (5), and cyclopropenes (6) reveal that the isodesmic substituent stabilization energies of 1, 3, and 5 relative to alkenes are correlated with group electronegativities with slopes of -15.1, -10.6, and -1.8, respectively, at the HF/6-31G * +ZPVE/HF/6-31G * level, corresponding to a successive decrease in polar character of the cumulenes in this order. Isomerization energies of 3 to 4 show that the relative stabilities of substituted diazomethanes and diazirines are dominated by the stabilization of diazomethanes by electropositive substituents