Gas Phase Studies of Organic Reaction Mechanisms. An Experiment and Ab Initio Study: The Development of Ionic Platforms for Chemistry

在美国国家科学基金会化学部有机动力学项目的支持下，在本科院校研究项目中，Scott Gronert 教授将在旧金山州立大学使用电喷雾质谱作为诊断仪器，对气相双阴离子进行研究。 气相离子界已广泛研究单阴离子反应物，经常遇到的问题是无法检测中性产物。 这项工作提供了一个解决方案：使用双阴离子，其中中性产物实际上是单阴离子，而不是中性离子，因此可以通过质谱法检测。 以这种方式，例如，亲核取代和消除之间的支化比变得可以通过实验确定。 这项工作将得到从头计算研究的支持。 现在可以在非常基础的层面上理解取代和消除，这是所有本科有机化学学生都熟悉的众所周知的反应。 这项工作将比较这些和其他类型的气相反应的实验产率和理论计算的产物产率。 该项目每年将涉及 4-6 名学生，所有人都将接触到理论与实验之间的相互作用。

With support from the Organic Dynamics Program of the Chemistry Division of NSF, within the Research in Undergraduate Institutions Program, Professor Scott Gronert will conduct research on gas phase dianions, using electrospray mass spectrometry as the diagnostic instrument, at San Francisco State University. The gas phase ion community has worked extensively with monoanion reactants, and a problem frequently encountered is inability to detect the neutral products. This work offers a solution: use dianions, from which the neutral products will actually be monoanions, not neutrals, and thus detectable by mass spectrometry. In this way branching ratios between nucleophilic substitution and elimination, for example, become determinable experimentally. The work will be supported by ab initio computational studies. Understanding of substitutions and eliminations, well-known reactions familiar to all students of undergraduate organic chemistry, is now possible at a very fundamental level. This work will compare experimental yields and theoretically calculated product yields for gas-phase reactions of these and other types. The project will involve 4-6 students per year and all will be exposed to the interplay between theory and experiment.