Mechanistic Investigations into Fundamental Organic Reactions

原型离子气相反应的机理将被研究，关键和/或不寻常的反应中间体将被表征气相离子分子技术。这项工作有两个重点，都集中在气相阴离子的化学性质上。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，在这个类别中，将研究过氧化物中氧原子上的SN2反应。此外，氮、氟和氯的取代反应将继续进行。第二部分是对双离子自由基阴离子的研究。这些新发现的物种在分子的不同原子上有分离的自由基和阴离子位点。将开发一些新的合成双离子自由基阴离子的途径，并对这些物种的反应性进行研究。这项来自有机动力学计划的拨款支持了匹兹堡大学约瑟夫·格拉博夫斯基教授的工作。气相离子反应的详细步骤（或机理）将通过专门的技术加以研究。这些反应可以与在溶液中进行的反应进行比较，以确定溶剂对反应的影响，溶剂对反应有深远的影响。阴离子与分子中的氧、氮、氟和氯原子的反应将被研究。此外，还将研究一类新型化合物双离子阴离子的合成和反应。这些新物种在不同的原子上有一个单位的负电荷和一个非成键电子。

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.