Dynamic Behavior Structure and Reactivity of Selfassembled Carbanionic Species

自组装碳负离子的动态行为结构和反应性

• 批准号: 1058035
• 负责人: Gideon Fraenkel
• 金额: $ 36万
• 依托单位: Ohio State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-09-15 至 2015-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1058035&HistoricalAwards=false
• 关键词: Dynamic; Behavior; Structure; Reactivity; Selfassembled

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.

化学结构，动力学和机制计划的这一奖项支持吉迪恩教授的工作。俄亥俄州州立大学的Fraenkel对碳负离子和碳负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，旨在以简单的方式揭示结构和动力学行为的特定方面。使用NMR、X射线晶体学和DFT建模研究结构。通过对核磁共振谱线的分析，揭示了平衡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负离子转化、碳锂键和配体锂键的相互交换和聚集体相互转化等动力学过程。感兴趣的结构方面包括由于阴离子和阳离子的取向对碳负离子内的共轭程度的影响。这些研究将应用于二氢吡啶锂盐。 其他研究涉及一种新的可能制备梯形聚合物。该计划的更广泛的方面涉及培训大学生的机会，包括妇女和代表性不足的少数民族成员在各种复杂的技术，这将有助于他们准备在工业或学术界的职业生涯。 大学生一直参与研究。 在俄亥俄州州立大学的化学系和工业界，与世界各地的团体就动态NMR问题以及Fraenkel集团开发的化学进行了广泛的合作。所有这些互动为小组成员提供了良好的联系。