Mechanistic Investigations into Fundamental Organic Reactions

基本有机反应的机理研究

• 批准号: 9407080
• 负责人: Joseph Grabowski
• 金额: $ 28.3万
• 依托单位: University of Pittsburgh
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1994
• 资助国家: 美国
• 起止时间: 1994-06-01 至 1997-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9407080&HistoricalAwards=false
• 关键词: Mechanistic; Investigations; into; Fundamental; Organic

9407080 Grabowski Univ. of Pittsburgh The mechanisms of prototypical ionic gas-phase reactions will be studied and key and/or unusual reactive intermediates will be characterized by gas-phase ion-molecule techniques. The proposed work has two major thrusts, both of which focus on the chemistry of gas-phase anions. The first part will be directed to bimolecular substitution (SN2) reactions at non-carbon first row elements. For example, in this category, SN2 reactions on the oxygen atom in peroxides will be studied. In addition, substitution reactions on nitrogen, fluorine, and chlorine will be pursued. The second part will be directed to a study of distonic radical anions. These newly discovered species have the radical and anionic sites separated on different atoms in the molecule. A number of new synthetic routes to distonic radical anions will be developed and the reactivity of these species will be investigated. This grant from the Organic Dynamics Program supports the work of Professor Joseph J. Grabowski at the University of Pittsburgh. The detailed steps (or mechanisms) of ionic reactions in the gas-phase will be studied by specialized techniques. These reactions can be compared to those carried out in solution in order to determine the effect of solvent, which has a profound effect on the reaction. The reaction of an anionic species at oxygen, nitrogen, fluorine, and chlorine atoms in molecules will be investigated. In addition, the synthesis and reactions of distonic anions, a new type of species, will be pursued. These novel species have one unit of negative charge and one non-bonded electron on different atoms.

9407080 格拉博夫斯基大学。匹兹堡将研究原型离子气相反应的机制，并通过气相离子分子技术表征关键和/或不寻常的反应中间体。拟议的工作有两个主要重点，都集中在气相阴离子的化学上。第一部分将针对第一行非碳元素的双分子取代（SN2）反应。例如，在这一类别中，将研究过氧化物中氧原子上的SN2反应。此外，还将研究氮、氟和氯的取代反应。第二部分将针对二张力自由基阴离子的研究。这些新发现的物种在分子中的不同原子上具有分开的自由基和阴离子位点。将开发许多新的双张力自由基阴离子合成路线，并研究这些物质的反应性。 有机动力学计划的这笔赠款支持匹兹堡大学 Joseph J. Grabowski 教授的工作。将通过专门技术研究气相中离子反应的详细步骤（或机制）。这些反应可以与在溶液中进行的反应进行比较，以确定溶剂的影响，溶剂对反应有深远的影响。将研究阴离子物质与分子中的氧、氮、氟和氯原子的反应。此外，还将研究新型物种双张力阴离子的合成和反应。这些新物种在不同原子上具有一个负电荷单位和一个非键合电子。