Physical Organic Chemistry of Sm(II) Reagents

University Of Toledo, Toledo OH

Investigators

Abstract

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.