Dynamic Behavior Structure and Reactivity of Selfassembled Carbanionic Species

该奖项来自化学结构、动力学和机制项目，支持俄亥俄州立大学Gideon A. Fraenkel教授对碳离子和碳离子物种的结构和快速平衡动力学行为的研究。在这项工作中，制备了特定的有机锂化合物，其设计以简单的方式揭示结构和动态行为的特定方面。利用核磁共振、x射线晶体学和DFT模型对其结构进行了研究。通过核磁共振线形分析揭示了平衡状态下快速分子重组过程的动力学和机理。这些过程可能包括碳离子转化动力学、碳锂键动力学和配体锂键动力学、分别交换动力学和聚集体相互转化动力学。我们感兴趣的结构方面包括阴离子和正离子的取向对碳离子内共轭度的影响。这些研究将应用于二氢吡啶锂盐。其他研究涉及一种新的阶梯聚合物制备方法。该项目更广泛的方面包括为本科生（包括女性和代表性不足的少数民族成员）提供各种复杂技术的培训机会，这些技术将帮助他们为工业或学术界的职业生涯做好准备。大学生一直参与研究。我们与世界各地的研究小组进行了广泛的合作，包括俄亥俄州立大学化学系和工业界的动态核磁共振问题，以及Fraenkel小组开发的化学。所有这些互动都为小组成员提供了良好的联系。

This award from the Chemical Structure, Dynamics and Mechanisms Program supports the work of Professor Gideon A. Fraenkel of Ohio State University on the structure and fast equilibrium dynamic behavior of carbanions and carbanionic species. In the work particular organolithium compounds are prepared which are designed to reveal in simple fashion specific aspects of structure and dynamic behavior. Structures are investigated using NMR, X-ray crystallography and DFT modeling. The kinetics and mechanisms of fast molecular reorganization processes at equilibrium are revealed from NMR line shape analysis. These processes may include the dynamics of carbanionic inversion, carbon-lithium bond and ligand lithium bond, exchange respectively and aggregate interconversion. Aspects of structure of interest include the effect on degree of conjugation within the carbanion due to orientation of anion and cation. These studies will be applied to lithium salts of dihydropyridines. Other studies involve a new possible preparation of ladder polymers.The broader aspects of this program involve opportunities to train undergraduates including women and members of underrepresented minorities in a variety of sophisticated techniques which will help them prepare for careers in industry or academia. Undergraduates have always been involved in the research. There is extensive collaboration with groups around the world, within the Chemistry department here at Ohio State University and in industry on dynamic NMR problems and as well as on chemistry developed by the Fraenkel group. All these interactions provide excellent contacts for members of the group.