Physical Organic Chemistry of Sm(II) Reagents

Sm(II) 试剂的物理有机化学

• 批准号: 0094091
• 负责人: Robert Flowers
• 金额: $ 29.5万
• 依托单位: University of Toledo
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-01-01 至 2001-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0094091&HistoricalAwards=false
• 关键词: Physical; Organic; Chemistry; Sm; II

With this new award the Organic and Macromolecular Chemistry Program supports the work of Dr. Robert A. Flowers at the University of Toledo in Toledo, Ohio. The research aims to develop a fundamental understanding of the equilibria and kinetics of the reactions involved in the use of Sm(II) reagents as reducing agents in organic chemistry. The work will involve determining the structures and aggregation states of SmI2 reducing agents in solution, and the influence of cosolvent (ligands) on the reactivity of the reagents, as well as developing a bulk electrolysis method to make the reductions catalytic in Sm. A variety of physical methods will be used, including vapor pressure osmometry, isothermal titration calorimetry, vis/uv absorption spectrometry, stopped flow kinetic methods, electrochemistry, and x-ray crystallography.The proposed research involves studies to understand the behavior of an important class of reducing agents based on Sm(II) which are used by organic chemists to carry out useful syntheses. The work is expected to lead to improved reaction conditions with higher yields of desired product and less undesired byproducts, and may lead to new reducing systems using electricity and only very small (catalytic) amounts of samarium. The work is expected to provide excellent training for the students involved.

通过这个新的奖项，有机和大分子化学计划支持俄亥俄州托莱多市托莱多大学的罗伯特·a·弗劳尔斯博士的工作。本研究旨在对有机化学中使用Sm（II）试剂作为还原剂所涉及的反应的平衡和动力学有一个基本的了解。这项工作将包括确定溶液中sm2还原剂的结构和聚集状态，以及助溶剂（配体）对试剂反应性的影响，以及开发一种体电解方法，使还原在Sm中具有催化作用。将使用各种物理方法，包括蒸汽压渗透法，等温滴定量热法，可见/紫外吸收光谱法，停止流动动力学方法，电化学和x射线晶体学。拟议的研究包括研究了解一类重要的基于Sm（II）的还原剂的行为，这些还原剂被有机化学家用于进行有用的合成。这项工作有望改善反应条件，提高所需产物的产量，减少不需要的副产物，并可能产生新的还原性系统，只使用电力和非常少量的（催化）钐。这项工作有望为参与的学生提供良好的培训。