Organic Ion-Molecule Chemistry

有机离子/分子反应将在气相中用傅里叶横流质谱仪和变温流动余辉-三重四极杆装置(190℃到400℃)进行研究。结果将与凝聚介质中的结果进行对比，并辅之以从头算分子轨道和密度泛函理论计算。将特别关注抗芳香族化合物、活性中间体和两性离子。以前，长寿命的环丙烯阴离子是在气相和溶液中产生的。这些物种通常在所有入门的有机化学教科书中都有讨论，因为它们具有根本的意义，并可能成为新材料的潜在来源。在这一授权期内，计划对环丙烯基阴离子衍生物进行光谱表征，并探索它们的反应性和结构。还将获得各种抗芳香族和同系抗芳香族化合物(离子和中性)的能量学，以便更好地了解这些长期追求但难以捉摸的物种。活性中间体在理解化学反应中起着核心作用，研究它们的反应性和能量学将受到相当大的重视。除了一些应变环化合物外，还将检查一些具有重要技术意义的中间体。最近开发了一种通用的、高度选择性的方法，用于在气相中制备自由基阴离子，这将促进这项工作的大部分。最后，我们将考察静电效应。这些相互作用在从有机合成、材料设计和层析到分子识别、酶结构和药物开发的众多领域中都非常重要。最近，第一个两性离子及其在气相中的中性离子被制备出来。这使得探索偶极离子的结构、反应性和能量学成为可能，开发模型来解释两性离子物种，并更好地了解静电效应。有了这个基于成就的续展奖，有机化学和高分子化学项目支持了明尼苏达大学双子城大学史蒂文·R·卡斯教授正在进行的工作。研究的重点是了解反应性有机中间体的反应性和热力学性质。试图了解控制气体和液体中几种类型反应的基本因素的化学家将对这项工作感兴趣，并将为研究生和本科生提供有价值的研究培训。

Organic ion/molecule reactions will be explored in the gas phase with a Fourier transfolm mass spectrometer and a variable temperature flowing afterglow-triple quadrupole apparatus (190 C to 400 C). The results will be contrasted to those in condensed media and supplemented with ab initio molecular orbital and density functional theory calculations. Particular attention will be focused on antiaromatic compounds, reactive intermediates, and zwitterionic ions. Previously, long-lived cyclopropenyl anions were generated in the gas phase and solution. These species in general are discussed in all introductory organic chemistry textbooks because they are of fundamental interest and may serve as potential sources of novel materials. During this grant period, spectroscopically characterizing cyclopropenyl anion derivatives and probing their reactivities and structures are planned. The energetics of a variety of antiaromatic and homoantiaromatic compounds (ions and neutrals) also will be obtained so that these long sought after but elusive species can be better understood. Reactive intermediates play a central role in understanding chemical reactions and considerable emphasis will be placed on studying their reactivity and energetics. Some technologically important intermediates will be examined in addition to a number of strained ring compounds. Much of this work will be facilitated by the recent development of a general and highly selective method for preparing radical anions in the gas phase. Finally, electrostatic effects will be examined. These interactions are extraordinarily important in a wealth of areas ranging from organic synthesis, material design and chromatography, to molecular recognition, enzyme structure, and drug development. Recently, the first zwitterionic ion and its neutral counterpart in the gas phase were prepared. This makes it possible to explore the structure, reactivity, and energetics of dipolar ions, develop models to explain zwitterionic species, and obtain a much better understanding of electrostatic effects.With this Accomplishment-Based Renewal award the Organic and Macromolecular Chemistry Program supports the ongoing work of Professor Steven R. Kass at the University of Minnesota- Twin Cities. The research focuses on understanding the reactivities and thermodynamic properties of reactive organic intermediates. The work will be of interest to chemists trying to understand the fundamental factors which control several types of reactions in gases and liquids, and will provide valuable research training to both graduate and undergraduate students.