Invited Talk 21st International Conference on Biological Inorganic Chemistry 2025

Reaction Mechanisms of Metal-Oxygen Compounds by Density Functional Theory: Compound I and II Examples (122151)

Kyung-Bin Cho 1
  1. Jeonbuk National University, Jeonju, JEOLLABUKDO, South Korea

Our research group specializes in finding the reaction mechanisms of reactions involving catalysts and substrates found in a biomolecular or biomimetic settings, which is usually inorganic, first-row transition metal species interacting with some form of oxygen and an organic substrate. Depending on the time allotted, this talk will focus on two of these areas. First is describing the reaction mechanism of a halogenation reaction performed by a Mn(IV)OH porphyrin cation species.1 This species would be a (synthetic protonated) Mn analogue to Cytochrome P450’s so-called Compound I species. In presence of Cl- ions, this compound can catalyze halogenation of organic substrates such as naphthalene. A reaction mechanism of this reaction, based on DFT calculations, will be presented.2 Second is the naphthalene di-oxygenation by synthetic Fe-Compound II. Compound II is a (probably protonated) high-valent Fe(IV)O compound which we found forms two carbonyl groups on naphthalene upon reaction with six synthetic Compound II catalysts. Also here, we describe a plausible reaction mechanism accounting for the 1:6 (substrate:catalyst) stoichiometry.

Funding: NRF of Korea Basic Science RS-2021-NR058689 and MoE LAMP Program RS-2024-00443714.

  1. Zhang, L.; Seo, M. S.; Choi, Y.; Ezhov, R.; Maximova, O.; Malik, D. D.; Ng, M.; Lee, Y.-M.; Sarangi, R.; Pushkar, Y. N.; Cho, K.-B.; Nam, W. J. Am. Chem. Soc., 2023, 145, 8319−8325.
  2. Zhang, L.; Russelisaac Premakumari, S.; Ng, M.; Zhang, J.; Lee, Y.-M.; Fukuzumi, S.; Cho, K.-B.; Nam, W. Submitted.