Mechanistic Investigations into Fundamental Organic Reactions

9407080 Grabowski匹兹堡大学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/或不寻常的活性中间体。拟议的工作有两个主要的推动力，这两个都集中在气相阴离子的化学。第一部分将针对非碳第一行元素的双分子取代（SN 2）反应。例如，在这一类别中，将研究过氧化物中氧原子上的SN 2反应。此外，还将进行氮、氟和氯的取代反应。第二部分是对二阶自由基负离子的研究。这些新发现的物种在分子中的不同原子上具有分离的自由基和阴离子位点。一些新的合成路线，distonic自由基阴离子将被开发和这些物种的反应性将被调查。 来自有机动力学计划的这笔赠款支持匹兹堡大学约瑟夫·格拉博夫斯基教授的工作。气相中离子反应的详细步骤（或机制）将通过专门技术进行研究。可以将这些反应与在溶液中进行的反应进行比较，以确定溶剂的影响，溶剂对反应具有深远的影响。将研究阴离子物种与分子中的氧、氮、氟和氯原子的反应。此外，还将研究一类新物种--二阶阴离子的合成和反应。这些新物种在不同的原子上有一个负电荷单元和一个非键合电子。

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.