Structure and Reorganization Dynamics of Self Assembled Carbanionic Species

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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.