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

在这个由化学部化学结构、动力学和机制项目资助的项目中，霍巴特和威廉史密斯学院的Walter J. Bowyer开发了使用原位显微技术研究表面反应动力学的策略。铟介导的烯化反应（IMA）的应用已被证明对合成化学家有广泛的好处，但在铟表面形成有机铟中间体的机制和速度却很少受到关注。测量这些非均相反应的速率常数是困难的，因为金属的活性表面积在反应过程中不断变化。Bowyer教授和他的学生最近开发了一种测量铟表面反应速率的方法，该项目将该策略扩展到确定IMA的非均相速率常数和激活能量。他们将这些动力学研究与核磁共振光谱相结合，以确定在反应中形成的有机铟中间体。通过对溶媒效应的解释和对反应机理的阐明，使合成条件的设计更加合理。铟介导的烯丙基化（IMA）反应在碳碳键的形成中起着重要的作用。这些反应通常在水中进行，产率高，产物结构正确，具有环保化学的优点。研究IMA反应的创造性显微方法的发展为研究反应的速度和程度提供了一种独特的手段。霍巴特和威廉史密斯学院强调研究是本科教育的基础和顶峰。该项目将进一步加强学院培养学生从事科学事业的能力。在夏季和学年期间工作的学生将参与该研究项目的所有阶段：实验设计，性能，数据解释和结果传播。

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.