Structure and Reorganization Dynamics of Self Assembled Carbanionic Species

自组装碳负离子的结构和重组动力学

• 批准号: 0077605
• 负责人: Gideon Fraenkel
• 金额: --
• 依托单位: Ohio State University Research Foundation -DO NOT USE
• 依托单位国家: 美国
• 项目类别: Continuing grant
• 财政年份: 2000
• 资助国家: 美国
• 起止时间: 2000-07-01 至 2003-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0077605&HistoricalAwards=false
• 关键词: Structure; Reorganization; Dynamics; Self; Assembled

With this award the Organic and Macromolecular Chemistry Program continues its support for the work of Gideon A. Fraenkel in the Department of Chemistry at Ohio State University in Columbus, Ohio. The work is aimed at understanding the details of the structures and solution dynamics of a variety of organolithium compounds, using a combination of synthesis, dynamic NMR, x-ray crystallography, and gradient corrected Density Functional Theory. The questions to be addressed include: 1) What are the solution structures of ion-paired organolithium compounds? 2) To what extent does stereochemical restriction by a pendant ligand perturb conjugation within allylic lithium compounds? 3) Does heavy alkyl substitution affect conjugation? and 4) Does Li ion coordination to a remote C-C double bond affect RLi addition?Organolithium compounds self assemble into equilibrium mixtures of rapidly interconverting species which vary in aggregation and solvation. Understanding the details of the rates and equilibria of these compounds is expected to improve the ability of organic chemists to employ them to carry out useful organic syntheses, for example in the production of improved rubber for tires. The combination of synthesis, spectroscopy, and theory should provide valuable training for the students involved in the research.

有了这个奖项，有机和高分子化学计划继续支持吉迪恩A。Fraenkel在俄亥俄州哥伦布市的俄亥俄州立大学化学系。 这项工作的目的是了解各种有机锂化合物的结构和溶液动力学的细节，使用合成，动态NMR，X射线晶体学和梯度校正密度泛函理论的组合。 需要解决的问题包括：1）离子配对有机锂化合物的溶液结构是什么？2)在烯丙基锂化合物中，侧链配体的立体化学限制在多大程度上扰乱了共轭？3)重烷基取代会影响共轭吗？锂离子配位到远端的C-C双键上是否影响RLi加成？有机锂化合物自组装成平衡混合物的快速相互转化的物种，不同的聚集和溶剂化。 了解这些化合物的速率和平衡的细节有望提高有机化学家利用它们进行有用的有机合成的能力，例如在生产改进的轮胎橡胶中。 综合，光谱学和理论的结合应该为参与研究的学生提供有价值的培训。