Insights from Combined Static and Dynamic Calculations

Exploring Cu(II)–oxyl Formation Mechanisms: Insights from Combined Static and Dynamic Calculations 

Inspired by the selective C–H bond cleavage abilities of monooxygenases such as pMMOs and LPMOs, which contain a 'histidine brace' and copper species, our group synthesized a Cu–UiO–67 metal-organic framework (MOF) with histidine ligands. H₂O₂ is widely utilized to activate Cu MOFs. However, the reaction mechanism of the Cu(I) oxidation reaction remains controversial.

In this talk, AIMD simulations along with static DFT calculations were applied to elucidate the crucial role of a Cu(II)–(OH)₂ intermediate in Cu(II)–oxyl formation. Additionally, we investigated the impact of solvent, specifically water and acetonitrile, on the reaction mechanism using AIMD simulations.

A conformational search tool, CREST, was also used to explore different Cu-intermediates and coordination numbers leading to Cu(II)–oxyl. Our results show that some intermediates prefer reacting with the ligand rather than forming a Cu(II)-oxyl, providing guidance for catalyst design. 

September, 2sc 2024 at ICTAC2024, Seville, Spain. 

https://www.cecam.org/workshop-details/frontiers-of-coarse-grained-models-from-new-developments-to-modeling-dynamics-assemblies-and-macromolecular-machines-1311