Physical Organic Chemistry of Sm(II) Reagents

有了这个新的奖项，有机和高分子化学计划支持博士罗伯特A。俄亥俄州托莱多的托莱多大学的鲜花。 该研究的目的是发展一个基本的理解的平衡和动力学的反应中使用的Sm（II）试剂作为还原剂在有机化学。 本工作将涉及确定SmI 2还原剂在溶液中的结构和聚集状态，以及助溶剂（配体）对试剂反应性的影响，以及开发一种本体电解方法，使Sm的催化还原。 将使用各种物理方法，包括蒸汽压渗透压法，等温滴定量热法，维斯/紫外吸收光谱法，停流动力学方法，电化学，和X-射线晶体学，拟议的研究涉及研究，以了解一类重要的还原剂的行为基于Sm（II）的有机化学家进行有用的合成。 这项工作预计将导致改善反应条件，提高所需产物的产率，减少不需要的副产物，并可能导致新的还原系统使用电力和只有非常少量的钐（催化）。 预计这项工作将为有关学生提供良好的培训。

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.