SusChEM: Powerful and Tunable Electron Donors for Reduction Chemistry and Catalysis

本课题由化学系化学结构、动力学和机理B项目资助，Dennis L. Lichtenberger和Jon T.亚利桑那大学化学和生物化学系的Njardarson和DennisH。普渡大学化学系的埃文斯正在开发能够在非极性溶剂中提供电子的分子化学。 这种强电子供体分子可能会开启许多新的化学转化和催化过程。 更强大和可调的电子供体的发展对化学和社会的广泛领域产生了广泛的影响，从添加到合成有机化学和天然产物化学的工具箱到洞察清洁和可持续燃料的催化生产，这是当今科学面临的重大挑战之一。 该项目结合了Njardarson教授（有机合成），Lichtenberger教授（无机化学，光谱学，热力学和机理）和Evans教授（电化学）的互补专业知识，并受益于与其他合成和理论化学家的合作。 该项目也得到了广泛的社区参与。 有大量美国原住民学生的学校的教师参与了这项研究。这项研究使用气相光电子能谱法研究了具有双环胍配体的双金属配合物，双环胍配体是迄今已知的最强的电子供体。本计画利用一系列合成、光谱、电化学和计算技术，研究这类电子供体的结构、动力学和机制。 该项目的具体目标是：（1）研究有机化学中使用现有电子供体难以或不可能发生的电子转移反应，如芳基氯的加氢脱卤，以消除环境中多氯联苯和其他有机卤化物的毒性;（2）表征电催化过程，如强供体将质子还原为氢。 这类分子内的化学修饰正在进行，以产生一系列电子供体能力，用于商业利益的选择性化学转化。

In this project funded by the Chemical Structure, Dynamics and Mechanisms B Program of the Chemistry Division, Professors Dennis L. Lichtenberger and Jon T. Njardarson of the Department of Chemistry and Biochemistry at the University of Arizona and Professor Dennis H. Evans of the Department of Chemistry at Purdue University are developing the chemistry of molecules with the ability to donate electrons in non-polar solvents. Such strong electron donor molecules may unlock many new chemical transformations and catalytic processes. The development of more powerful and tunable electron donors has broad impacts on wide areas of chemistry and society, from additions to the toolbox of synthetic organic chemistry and natural products chemistry to insights into the catalytic production of clean and sustainable fuels, which is one of the grand challenges facing science today. The project combines the complementary expertise of Professor Njardarson (organic synthesis), Professor Lichtenberger (inorganic chemistry, spectroscopy, thermodynamics and mechanisms) and Professor Evans (electrochemistry), and benefits from collaborations with other synthetic and theoretical chemists. The project also has broad community participation. Teachers at schools with large Native American student populations participate in the research.The research uses gas phase photoelectron spectroscopy to study dimetal complexes with bicyclic guanidinate ligands that are the strongest electron donors yet known. This project investigates the structure, dynamics and mechanisms of this class of electron donors using a range of synthetic, spectroscopic, electrochemical, and computational techniques. Specific aims of the project are to: (1) investigate electron transfer reactions in organic chemistry that are difficult or impossible with current electron donors, such as the hydrodehalogenation of aryl chlorides to detoxify polychlorinated byphenyls and other organic halides in the environment, and (2) characterize electrocatalytic processes such as the reduction of protons to hydrogen by strong donors. Chemical modifications within this class of molecules are being pursued to produce a range of electron donor abilities for selective chemical transformations of commercial interest.