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.