C16H14SNF分子中不共面轭环上π轨道通过键的相互作用的研究

本文根据我们测定的C16H14SNF(1)和C16H16SNF(2)晶体结构数据,用MNDO2方法进行分子轨道研究,发现1和2的几何构型虽然相近,但其分子轨道中的原子轨道组成有着质的差异:在HOMO和临近HOMO的占据分子轨道中,2的两个苯环的π轨道彼此没有相互作用;1的两个夹角为80°的苯环的π轨道同时出现在一个分子轨道中,彼此通过C=N-键导通,显示出相互作用,与实验观察到的核磁共振谱一致.

Interaction between \p-orbitals of non-coplanar conjugated rings through bonds in molecule of C16H14SNF

Quantum chem. calcns. on 2-methyl-4-(p-fluorophenyl)-2,3-dihydrobenzo1,5]thiaazatropolone and 2-methyl-4-(p-fluorophenyl)-2,3,4,5-tetrahydrobenzo1,5]thiaazatropolon e were performed by means of the MNDO/2 method. The geometries of the compounds were taken from crystal structure data. Although the geometries of I and II are similar, the MO's of the 2 mols. differ significantly with respect to the coefficients of AO's in the MO's. There is no interaction between the p-orbitals of the 2 benzene rings in mol. II, but there is interaction between the p-orbitals (HOMO and MO's closed to HOMO) of the 2 aromatic rings in mol. I The interaction is through the C:N bond. The result is consistent with NMR measurements.