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

在这个由化学系化学结构、动力学和机制B计划资助的项目中，亚利桑那大学化学和生物化学系的Dennis L.Lichtenberger和Jon T.Njardarson教授以及普渡大学化学系的Dennis H.Evans教授正在开发具有在非极性溶剂中给出电子的能力的分子化学。如此强大的电子给体分子可能会开启许多新的化学转化和催化过程。更强大和可调节的电子给体的发展对化学和社会的广泛领域产生了广泛的影响，从合成有机化学和天然产物化学工具箱的添加到对清洁和可持续燃料的催化生产的洞察，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、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。该项目也有广泛的社区参与。拥有大量美洲原住民学生的学校的教师参与了这项研究。该研究使用气相光电子能谱来研究双环胍类配体的双金属络合物，这些配体是迄今已知的最强的电子给体。本项目利用一系列的合成、光谱、电化学和计算技术来研究这类电子给体的结构、动力学和机理。该项目的具体目标是：(1)研究有机化学中的电子转移反应，这些反应对于目前的电子给体来说是困难的或不可能的，例如芳基氯化物的加氢脱卤化以消除环境中苯基和其他有机卤化物对多氯联苯的毒性，以及(2)表征电催化过程，例如由强电子给体将质子还原为氢。这类分子正在进行化学修饰，以产生一系列的电子供体能力，以进行具有商业价值的选择性化学转化。

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.