RUI: Continuing Studies of the Kinetics and Mechanism of the Reaction of Allyl Halides at Indium Surfaces

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In this project funded by the Chemical Structure, Dynamics, and Mechanisms Program of the Chemistry Division, Walter J. Bowyer of Hobart and William Smith Colleges develops strategies for the use of in situ photomicroscopy for the study of surface reaction kinetics. Applications of indium mediated allylations (IMA) have proven of wide benefit to synthetic chemists, but the mechanism and rates of the formation of organoindium intermediates at indium surfaces have received very little attention. The measurement of rate constants for these heterogeneous reactions is difficult because the active surface area of the metal changes continuously during the reactions. Professor Bowyer and his students recently developed a method for measuring rates of reaction at indium surfaces and this project extends that strategy to determining heterogeneous rate constants and energies of activation of IMA. They combine these kinetic studies with NMR spectroscopy to identify the organoindium intermediates formed in the reaction. The improved understanding of IMAs facilitate more rational design of synthetic conditions by explaining solvent effects and illuminating the mechanism of the reaction. Indium-mediated allylation (IMA) reactions are important in the formation of carbon-carbon bonds. These reactions generally proceed in water with high yield and correct product configuration, offering the benefits of environmentally-friendly chemistry. The development of creative photomicrosocpy methods to examine the IMA reactions provides a unique means of investigating the speed and extent of reaction. Hobart and William Smith Colleges emphasize research as both the foundation and the pinnacle of undergraduate education. This project will further strengthen the Colleges' abilities to prepare students for careers in science. The students working during the summer and the academic year will participate in all phases of this research project: experimental design, performance, data interpretation, and dissemination of results.