With ever-growing energy needs it is imperative that we find clean and renewable energy sources. One of the best options is believed to be solar energy, which would require the capture of sunlight and its conversion to energy, for example using photovoltaics, followed by the storage of that energy. One way to store the generated energy is in the H-H bond, with the hydrogen atoms coming from water, with the oxygen gas as a byproduct, making a carbon-free energy source. Splitting water requires the oxidation of water, giving oxygen gas and protons, then the reduction of the protons to hydrogen gas where the first reaction has been considered the bottleneck. 1-distal was found to be a robust water oxidation catalyst with a turnover number of 2700 by Thummel1; interestingly 1-proximal, the isomer that is a hydrogen bond acceptor, was not an active catalyst. As computed by Yagi et al2 the LUMO of 1-distal has a large coefficient at the ruthenium oxo, the ideal location, but the LUMO of 1-proximal has large coefficients on on the napthyridine ring, which could lead to attack and degradation of the ring. Our hypothesis was that addition of bulky R groups on the napthyridine ring could disfavor this degradation pathway, and give oxidatively resistant ligands. The synthesis and water oxidation activity will be discussed for complexes 2-5 proximal and 2-5 distal. 1) Boyer, J. L.; Polyansky, D. E.; Szalda, D. J.; Zong, R. F.; Thummel, R. P.; Fujita, E. Angew. Chem. Int. Edit. 2011, 50, 12600. 2) Hirahara, M.; Ertem, M. Z.; Komi, M.; Yamazaki, H.; Cramer, C. J.; Yagi, M. Inorg. Chem. 2013, 52, 6354.

Synthesis and water oxidation activity of sterically hindered [Ru(Cl)(terpy)pyridylnapthyridine] Cl analogs; an attempt at fluorinated oxidatively resilient ligands

251st National Meeting (2016)

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