Organic Ion-Molecule Chemistry

有机离子分子化学

• 批准号: 0107797
• 负责人: Steven Kass
• 金额: --
• 依托单位: University of Minnesota-Twin Cities
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-11-01 至 2007-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0107797&HistoricalAwards=false
• 关键词: Organic; Ion; Molecule; Chemistry

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.

有机离子/分子反应将在气相中用傅里叶变换质谱仪和变温流动余辉三重四极装置（190 ℃至400 ℃）进行探索。结果将与凝聚介质中的结果进行对比，并补充从头计算分子轨道和密度泛函理论计算。特别注意力将集中在反芳族化合物，活性中间体，和两性离子。以前，长寿命的环丙烯基阴离子在气相和溶液中产生。这些物种一般在所有介绍有机化学教科书中讨论，因为它们具有根本的兴趣，并可能作为新材料的潜在来源。在此期间，计划用光谱法表征环丙烯基阴离子衍生物并探测其反应性和结构。各种反芳香族和高反芳香族化合物（离子和中性物）的能量学也将获得，以便更好地理解这些长期追求但难以捉摸的物种。反应性中间体在理解化学反应中起着核心作用，相当大的重点将放在研究它们的反应性和能量学上。一些技术上重要的中间体将被检查，除了一些应变环化合物。最近发展的一种在气相中制备自由基阴离子的通用和高选择性的方法将促进这项工作。最后，将研究静电效应。这些相互作用在从有机合成、材料设计和色谱到分子识别、酶结构和药物开发的许多领域都非常重要。最近，在气相中制备了第一个两性离子及其中性对应物。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，并获得更好地理解静电效应。明尼苏达大学双城分校的卡斯。研究重点是了解反应性有机中间体的反应性和热力学性质。这项工作将感兴趣的化学家试图了解控制几种类型的反应在气体和液体的基本因素，并将提供有价值的研究培训，研究生和本科生。