桶烯及其相关分子同共轭性质的理论研究

Theoretical Studies on the Homoconjugation Effect of Barrelene and Related Molecules

在RHF/ 6 - 31G(d ,p) ,RHF/ 6 - 31+G(d ,p) ,MP2 / 6 - 31+G(d ,p)和B3LYP/ 6 - 31+G(d ,p)水平优化得到了桶烯和相关分子的平衡几何构型 .进一步用MP2 / 6 - 31G (d ,p) / /RHF/ 6 - 31G(d ,p) ,MP2 / 6 - 31+G(d ,p) / /RHF/ 6 - 31G + (d ,p)和B3LYP/ 6 - 31+G(d ,p) / /B3LYP/ 6 - 31+G(d ,P)水平计算桶稀、双环 [2 .2 .2 ]-辛二稀和双环 [2 .2 .2 ]-辛稀的气相氢化热 (ΔH0( 2 98K) ) ,气相氢化自由能 (ΔG0( 2 98K) )和同键反应芳香性稳定化能 (HASE) ,计算结果指出桶烯有较长的C(sp2 ) -C(sp3)单键 ,小的∠C -C =C键角和比较大的氢化热 ,同键反应芳香性稳定化能为正值 ,表明桶烯为反双环芳香性分子 ,实现了标题化合物反芳香性的几何。

The conformation,gas-phase hydrogenated enthalpy (ΔH 0 (298K) )and free energy(ΔG 0 (298K) )of barrelene and related molecules were calculated at the SCF and MP2 and B3LYP levels using 6-31G(d,p)and 6-31+G(d,p) basis sets. The homodesmic reaction aromatic stabilization energy(HASE) was also computed by using the same methods. The HASE was more Positiv values, indicating barrelene is anti-bicycloaromatic molecule. Thus the titled compound fulfills the geometrical and energetic criteria of aromaticity