Ionic Organic Reactions and Their Intermediates

本项目致力于新型碳正离子和铵离子的合成和研究。在稳定的离子条件下，超强酸会生成质子化的高取代苯化合物，如间二甲苯、间三甲苯和六甲基苯。难以捉摸的二、三和四偶氮甲烷二、三和四偶氮甲烷二、三和四偶氮甲烷将分别用从头算/GIAO-MP2计算建模，并在超强酸溶液中制备和表征。还将研究一些有趣的三氟甲基取代烯丙基阳离子和聚烯丙基阳离子以及若干硅基化铵离子，包括硅基化尿素、胍离子、甲酰胺和乙酰胺离子。通过氢/氘交换实验研究了N，N-二甲基亚胺离子（CH2=N(CH3)2+）和异丙基亚胺离子（CH3）2C=NH2+的超亲电活性。二烷基醚/聚（氟化氢）硫磷类似物即二烷基硫醚/聚（氟化氢）和三烷基膦/聚（氟化氢）配合物将作为新型离子液体进行制备和研究。有了这个奖项，有机和大分子化学项目支持了南加州大学化学系George A. Olah博士的研究。结合实验结构和力学研究与理论分析，奥拉教授和他的学生正在阐明化学过程的基本步骤。他们的研究集中在具有一个或多个正电荷的反应中间体的生成、结构和反应化学。这种新颖的中间体已涉及许多实验室和商业意义的过程。这些研究为选择性有机反应的设计和大规模石油化工过程中的现象（如催化裂化和烷基化反应）提供了重要的见解。

This project addresses the synthesis and study of novel carbocations and onium ions. Protonated highly-substituted benzenium dications such as m-xylene, mesitylene and hexamethylbenzene will be generated in superacids under stable ion conditions. The elusive bis-, tris- and tetradiazomethane di, tri- and tetracation, respectively, will be modeled with ab initio/GIAO-MP2 calculations and prepared and spectrally characterized in superacid solution. A number of interesting trifluoromethylsubstituted allyl cations and polyallyl cations and several silylated onium ions, including silylated urea, guanidinium ion, formamide and acetamide ions, will also be examined. Superelectrophilic activation of N,N-dimethylmethyleniminium ion, CH2=N(CH3)2+ and the isomeric isopropyleniminium ion, (CH3)2C=NH2+ will be investigated by hydrogen/deuterium exchange experiments. Sulfur and phosphorous analogs of dialkyl ether/poly(hydrogen fluoride) i.e dialkyl thioether/poly(hydrogen fluoride) and trialkyl phosphine/poly(hydrogen fluoride) complexes will be prepared and studied as new ionic liquids.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. George A. Olah of the Department of Chemistry at the University of Southern California. Combining experimental structural and mechanistic studies with theoretical analyses, Professor Olah and his students are elucidating fundamental steps in chemical processes. Their studies are focused on the generation, structure, and reaction chemistry of reactive intermediates bearing one or more positive charges. Such novel intermediates have been implicated in numerous processes of laboratory and commercial significance. These studies are providing important insights into the design of selective organic reactions and into the phenomena at play in large-scale petrochemical processes such as catalytic cracking and alkylation reactions.