【摘要】 运用G03W程序,在高精度理论水平(B3P86/6-311+G**)下,对母体转烯(Hypostrophene)及其BCO衍生物的单态、三态、开壳层单态的Cope重排体系进行了理论研究:对体系进行了相应的结构优化和频率计算,并进一步计算了体系的重排势垒、反应能量、核独立化学位移值等理论参数.文中首次提出具有四同芳香性的实例:转烯的Cope重排过渡态.计算同时表明BCO取代CH的行为使得进行Cope重排的反应物和过渡态的离域性、芳香性以及稳定性都得到很大的促进,这可以从前线轨道的成键以及延伸方面得到合理的解释.所得结果进一步验证了BCO基团的稳定性效应.更多还原

【Abstract】 Calculations on the normal singlet, triplet and open-shell singlet of hypostrophene, its BCO- analogues and the theoretical transition states for the Cope rearrangement at the B3P86/6-311+G** level have been done with G03W program. By discussing the geometries of the hypostrophene and its BCO-ana- logues, nucleus independent chemical shifts (NICS), the Cope barriers and the molecule orbitals, we got some interesting information. The transition state for the hypostrophene was the first neutral tetra- homoaromaticity case in recent papers. In the hypostrophene system, the replacements of CH by BCO caused theoretical transition states to be delocalized and aromatic energy minimized, resulting in enhance- ment of delocalization, aromaticity and stability of both reactants and transition states, which confirmed the BCO stabilization effects further.更多还原