Department of Chemistry, University of North Carolina, CB 3290, 27599-3290, Chapel Hill, NC.
J Am Soc Mass Spectrom. 1996 May;7(5):473-81. doi: 10.1016/1044-0305(95)00704-0.
The reactions of phenylium with water and ammonia and their methyl homologs have been investigated using a quadrupole ion trap and semiempirical molecular orbital calculations. The results indicate that both types of molecules react with phenylium through lone pair electrons even though, for methyl-containing compounds, insertion into a C-H bond would lead to more stable products. For the excited adducts formed by reaction with methyl-containing reactant neutrals, the only dissociation observed is loss of a methyl radical. Neutral losses of H2 or CH4, which are more thermodynamically stable, are not observed, which indicates that these reactions are either not kinetically competitive or have high energy transition states due to the fact that the reactions would need to occur via orbital symmetry forbidden 1,2 eliminations.
采用四极离子阱和半经验分子轨道计算方法研究了苯鎓与水和氨及其甲基同系物的反应。结果表明，尽管对于含甲基的化合物，插入 C-H 键会导致更稳定的产物，但这两种类型的分子都通过孤对电子与苯鎓反应。对于与含甲基反应物中性形成的激发加合物，仅观察到失去一个甲基自由基的离解。没有观察到更热力学稳定的 H2 或 CH4 的中性损失，这表明这些反应要么不是动力学竞争的，要么由于反应需要通过轨道对称禁阻的 1,2 消除来进行，因此具有高能量过渡态。
