Keynote Talk 21st International Conference on Biological Inorganic Chemistry 2025

Nonheme iron activation of O2: Intermediates, substrate oxidation, and rebound selectivity (122028)

David P Goldberg 1 , Sudha Yadav 1 , Jesse B Gordon 1 , Vishal Yadav 1 , Lyupeng Wen 1 , Sawyer Lyons 1 , Isabella Niedzwiecki 1
  1. Johns Hopkins University, Baltimore, MD, United States

Understanding how nonheme iron centers bind and activate O2, and carry out the selective oxidation of various substrates, is a major challenge in bioinorganic chemistry. Progress in this area has led to mechanistic insights for nonheme iron oxygenases, hydroxylases, halogenases, and related enzymes. Fundamental principles for the design of synthetic iron-based catalysts have also been revealed in these works. This presentation will focus on our recent results on the design and synthesis of nonheme iron complexes that incorporate first- and second-coordination sphere structural elements for binding and activating O2. Ligand design strategies that have led to the capture of O2-derived intermediates, including ferric-superoxo and high-valent ferryl-oxo species, will be described. With time permitting, a series of downstream ferric-hydroxo and related complexes will be discussed that react with carbon radicals through different, selective radical transfer, or “rebound” pathways. Mechanistic insights include the nature of possible intermediates in sulfur oxygenation mediated by nonheme iron enzymes such as the thiol dioxygenases, as well as the species and pathways involved in nonheme iron-mediated halogenation.

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  2. Gordon, J. G.; Albert, T.; Dey, A.; Sabuncu, S.; Siegler, M. A.; Bill, E.; Moënne-Loccoz, P.; Goldberg, D. P., J. Am. Chem. Soc., 2021, 143, 51, 21637–21647.
  3. Yadav, V.; Wen, L.; Rodriguez, R. J.; Siegler, M. A.; Goldberg, D. P., J. Am. Chem. Soc., 2022, 144, 45, 20641–20652.