1-三氯锡烷基-2,3-丁二烯和2-三氯锡烷基-1,3-丁二烯与甲醛反应的B3LYP研究

用密度泛函方法在B3LYP/6-31G^**水平上研究了1-三氯锡烷基-2,3-丁二烯和2-三氯锡烷基-1,3-丁二烯与甲醛的反应.优化得到各驻点的几何构型,通过振动分析和内禀反应坐标对过渡态进行了确认,解析了反应路径.并用SCRF(PCM)方法在同一水平上对在CH₂Cl₂溶液中的两反应进行了研究.计算了两反应在气相和CH₂Cl₂溶液中的活化能垒、自由能和平衡常数.结果表明,反应具有很强的选择性,主要得到1-三氯锡烷基-2,3-丁二烯与甲醛反应的产物.该结果与实验事实一致.

Theoretical Studies on Two Reactions of 1-Trichlorostannylbuta-2,3-butadiene and 2-Trichlorostannylbuta-1,3-butadiene with Formaldehyde by B3LYP

The two reactions of 1-trichlorostannylbuta-2,3-butadiene and 2-trichlorostannylbuta-1,3-butadiene with formaldehyde have been studied by using the density functional method at the B3LYP/6-31G ** level. The structures and energies of the stationary points were calculated to produce the activation barriers, free energy changes and equilibrium constants. The transition states were testified by using vibration analysis and IRC calculations. The two reactions in CH2Cl2 solvent at 1.013×105 Pa and 298.2 K have also been studied by the SCRF(PCM) method at the same level. The results show that the reactions take place with high regioselectivity and mainly produce the product of the reaction of the 1-trichlorostannylbuta-2,3-butadiene with formaldehyde.