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 Grabowski Univ。匹兹堡的原型离子气相反应的机制将进行研究，键和/或异常的反应性中间体将以气相离子 - 分子技术为特征。拟议的工作有两个主要的推力，这两者都集中在气相阴离子的化学上。第一部分将针对非碳第一行元素的双分子取代（SN2）反应。例如，在此类别中，将研究过氧化物中氧原子上的SN2反应。此外，将追求对氮，氟和氯的替代反应。第二部分将针对散开的自由基阴离子的研究。这些新发现的物种的自由基和阴离子位点在分子中的不同原子上分开。将开发出许多新的与散开的自由基阴离子的合成途径，并将研究这些物种的反应性。 有机动力学计划的这项赠款支持匹兹堡大学约瑟夫·J·格拉布洛夫斯基教授的工作。专用技术将研究气相中离子反应的详细步骤（或机制）。可以将这些反应与溶液中进行的反应进行比较，以确定溶剂的作用，这对反应具有深远的影响。将研究一个阴离子物种在分子中氧，氮，氟和氯原子上的反应。此外，将追求散开阴离子的合成和反应，即一种新型的物种。这些新型物种具有一个负电荷的单位，在不同原子上具有一个非键值电子。