Ionic Organic Reactions and Their Intermediates

将继续研究碳、硫和氢离子如BH6+和AlH6+在超强酸溶液中的制备、结构表征和反应活性。结构和反应性将通过核磁共振光谱进行表征，在可能的情况下，可分离的离子盐将被结晶并确定X射线晶体结构。理论计算将结合实验工作进行。将尝试新的方法来制备简单但难以捉摸的碳正离子-烯丙基、苯基、环己基和苯基-以及更复杂的聚阳离子，如2，4，6-三取代-1，3，5-三苯基(苯)三取代和甲基四(对异丙基)四聚阳离子。有了这一续期奖，有机和高分子化学项目将继续支持南加州大学化学系的George A.Olah和Golam Rasul博士。Olah博士在碳正离子或碳正离子方面获得诺贝尔奖的工作是基于他的观察，即这些被认为是有机反应中的活性中间体的不稳定有机物种实际上可以通过核磁共振进行光谱观察，并在低温下的溶液中研究它们的结构和反应，前提是人们拥有正确的溶剂和Lewis酸。这些研究将有助于更好地了解强酸中的亲电活性，并有望在有机化学中找到新的合成方法。这项工作还将为博士后和研究生提供宝贵的化学研究经验。┤╣_║╝？└？┤？`║╝？║/╝？╣？？╝？╣││？_║？┐┤？┤？？`▓/？？┤？？╝？/？/╣││？_║？┐┤？？┤？？`▓/？？┤？？╝？/？？%╣│╝？/？？║？？袁？╣/%？╝┐？？╣？║╝？╝？/╣││？_║？┐┤？？/└╣？╣？╝？袁╣？▓╣？%？？╣│/%║╝？║？╝？╣？╣？┴？╝，？元┐┤？元？┴╣%%╝？│？╣└？元？╝/╣╣？┐？┐%╣┤？└？%

Research involving the preparation, structural characterization, and reactivities of carboxonium, sulfonium and hydrido onium ions such as BH6+ and AlH6+ in superacid solutions will be continued. Structures and reactivities will be characterized by NMR spectroscopy, and where possible, isolable ionic salts will be crystallized and X-ray crystal structures determined. Theoretical calculations will be carried out in conjunction with the experimental work. New ways will be attempted to prepare simple but elusive carbocations - allyl, benzyl, cyclohexy, and phenyl - as well as more complex polycations such as 2,4,6-trisubstituted-1,3,5-tribenzyl (benzene) trications, and methanetetrakis(para-cumyl)tetrayl tetracation. With this renewal award, the Organic and Macromolecular Chemistry Program is continuing support for Drs. George A. Olah and Golam Rasul in the Department of Chemistry at the University of Southern California. Dr. Olah's Nobel Prize winning work on carbocations, or carbonium ions, was based on his observation that these unstable organic species, which had been proposed as reactive intermediates in organic reactions, could actually be observed spectroscopically by NMR and their structures and reactions studied in solution at low temperature, provided one had the right solvents and Lewis acids. These studies will provide a better understanding of electrophilic reactivity in strong acids, and are expected to lead to new synthetic methods in organic chemistry. The work will also provide valuable chemical research experience for postdoctoral and graduate students. ┤ ╣_║╝?└Á┤ ¢`¥©Á¥╣│ _Á¥©?┤¢ Â?╝ ¥©Á ║╝Á║/╝/¥╣? ? ?╝À/╣│ │?_║?┐┤¢ ¼©Á _Á¥©?┤??À` ▓/¢Á┤ ? ?╝À/?_Á¥/%%╣│ ╝Á/ÀÁ¥¢ ©/¢ ║?¥Á¥╣/% Â?╝ ┐¢Á ╣ ¥©Á ║╝Á║/╝/¥╣? ? ?╝À/╣│ │?_║?┐┤¢ ©/└╣À ╣¥Á╝Á¢¥╣À ▓╣?%?À╣│/% ║╝?║Á╝¥╣Á¢ ¿ ¥©╣¢ ┴?╝, ¢¥┐┤Á¥¢ ┴╣%% ╝Á│Á╣└Á ¥╝/╣╣À ┐¢ÁÂ┐% ╣ ┤Á└Á%