Dynamic Behavior Structure and Reactivity of Selfassembled Carbanionic Species

化学结构、动力学和机制项目的这一奖项支持俄亥俄州立大学的吉迪恩·A·弗拉恩克尔教授在碳负离子和碳离子物种的结构和快速平衡动态行为方面的工作。在这项工作中，特别制备了有机锂化合物，旨在以简单的方式揭示结构和动态行为的特定方面。用核磁共振、X-射线结晶学和密度泛函理论对其结构进行了研究。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反转、碳-锂键和配位体锂键的动力学、分别交换和聚集体相互转化。感兴趣的结构方面包括由于阴离子和阳离子的取向对碳离子内共轭程度的影响。这些研究将应用于二氢吡啶的锂盐。其他研究涉及一种新的可能的梯形聚合物的准备。该计划的更广泛的方面包括培训本科生，包括妇女和代表不足的少数族裔成员，掌握各种复杂的技术，帮助他们为在工业或学术界的职业生涯做准备。本科生一直都在参与这项研究。俄亥俄州立大学化学系和工业界在动态核磁共振问题和Fraenkel小组开发的化学方面与世界各地的小组进行了广泛的合作。所有这些互动为小组成员提供了极好的联系。

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.