摘要
简要综述了重主族多重键,尤其是重主族累积多烯化合物的合成及结构表征和理论研究方面的最新进展.使用Gaussian98量子化学计算程序包中的abinitio计算法(HF)、密度泛函数(B3LYP)和MP2法,在6 311G(d,p)和6 311+G(d,p)基组水平下,对磷杂硅杂丙二烯及其相关异构体进行了全优化几何构型的量子化学计算.计算结果表明:丙二烯型分子具有弯曲几何构型,在炔烃异构体中,含SiP和CC三键的异构体近乎为直线分子.含CSi三键的异构体是最不稳定的分子,且在硅原子上有强的棱锥化效应和明显的孤对电子特征.利用计算的分子总能量,原子净电荷分布和分子偶极矩对各标题的分子几何构型、物理和化学性质进行了分析和讨论,并由计算的相对稳定化能比较和确定了磷杂硅杂丙二烯及其相关异构体的相对稳定性,得到了含CP和SiP三键的异构体比相应的累积二烯异构体稳定的结论.
This paper briefly summarized the new progress of theoretical studies on synthesize and characterize the compounds with multiple bonds between heavier main group elements,especially heavy cumulenes.The phosphasilaallenes and related isomers have been calculated by using the calculating methods of quatum chemisty in Gaussion98 programme.The optimized geometries were obtained at several levels of theory(HF/6-311G(d,p),HF/6-311+G(d,p),B3LYP/6-311G(d,p),B3LYP/6-311+G(d,p),MP2/6-311G(d,p)).The result of calculations presented that the allenic system have a trans-bent geometries.In triple bonding isomer,Si≡P triple bonding and C≡P triple bonding isomers have a linearity geometry.C≡Si triple bonding isomers have a pyramidal geometry and lone pair character at silicon.The energies, atomic charges and dipole moment of the molecules have also been calculated,the relative stability of the all isomers have been carefully compared.The C≡P triple bonding isomers and Si≡P triple bonding isomers are more stable than cumulenes,C≡Si Triple bonding isomer is most unstable.
出处
《甘肃教育学院学报（自然科学版）》
2004年第1期48-53,共6页
Journal of Gansu Education College(Natural Science Edition)
