【摘要】 将激光解离／分子束流／飞行时间质谱仪结合起来设计的装置内，让激光解离石英反应室内的单质镍，并使产生的Ni+与连续喷入的酮类化合物分子束流反应，生成的产物离子经飞行时间质谱仪检测，发现在Ni+与酮的气相反应中，Ni+总是插入与酮羰基相连的C-C单键，然后发生分子内重排，裂解。根据如下的插入机理能很好地解释发生的反应：（1）Ni+插入酮分子中O=C-C的C-C单键；（2）β-H或β-烷基迁移至Ni+上；（3）失去中性分子得Ni+的络合物离子。更多还原

【Abstract】 In the equipment combining the Laser ablation, the molecular flow and the time-of-flight, the gas phase reactions of lase ablated Ni+ in a small quartz cell with molecular flows of ketones have been studied, and their product ions were detected by the time-of-flight mass spectrometry. It was discovered that Ni+ always inserts C-C single bonds O=C-C of ketones, then undergos intramolecular rearrangements and dissociation. The reaction can be expained by the following mechanism: (1) The inserion of Ni+ into O=C-C single bond; (2) A β-hydride shift for one of the alkyt and the acyl groups or a β-alkyl shift fiom acyl group to produce intermediate; (3) The competitive dissociation of intermediate to form product ion and neutral molecule.更多还原