Invited Talk 21st International Conference on Biological Inorganic Chemistry 2025

The Organometallic Chemistry of Nickel Enzyme Mimics (122205)

Liviu M Mirica 1
  1. University of Illinois at Urbana Champaign, Champaign, IL, United States

Aims: This presentation will focus on the chemistry related to two Ni-containing enzymes, acetyl-Coenzyme A synthase (ACS) and [NiFe] hydrogenase, which perform exquisite oxygen-sensitive organometallic chemistry in a biological environment.

Results: Recently, we have reported the development of catalytic and functional mimics of both [NiFe] hydrogenases and ACS.1-4

Conclusions: The novelty of our approach stems from the design of flexible multidentate ligands with mixed hard/soft donor atoms that allow the detection and characterization of both low- and high-valent organometallic Ni species, which are key reactive intermediates during catalysis.

 

  1. 1 Chakrabarti, S.; Sinha, S.; Tran, G. N.; Na, H.; Mirica, L. M., Characterization of Paramagnetic States in an Organometallic Nickel Hydrogen Evolution Electrocatalyst, Nature Commun., 2023, 14, 905, https://doi.org/10.1038/s41467-023-36609-7
  2. 2 Griego, L.; Woods, T. J.; Mirica, L. M., A Five-Coordinate Ni(I) Complex Supported by 1,4,7-Triisopropyl-1,4,7-triazacyclononane. Chem. Comm., 2022, 58, 7360-7363, https://doi.org/10.1039/d2cc02516g
  3. 3 Sinha, S.; Tran, G. N.; Na, H.; Mirica, L. M., Electrocatalytic H2 Evolution Promoted by a Bioinspired (N2S2)Ni(II) Complex. Chem. Comm., 2022, 58, 1143–1146, https://doi.org/10.1039/D1CC05139C
  4. 4 Nath, S. G., L; Mirica, L. M., The Mechanism of Acetyl-CoA Synthase Through the Lens of a Nickel Model System. submitted, ChemRxiv preprint DOI: https://doi.org/10.26434/chemrxiv-2025-4zxqp