Hemilabile Thio– and Selenoethers in Bis(benzimidazolyl)Amine Copper Complexes Relevant to the Active Sites of Copper-Dependent Monooxygenases

Summary, in English

Copper complexes supported by benzimidazole-based tetradentate neutral ligands featuring thio- and selenoether donors, resemble the coordination environment of the active site in copper dependent monooxygenases Dopamine-β-monooxygenase (DβM) and peptidylglycine-α-hydroxylating monooxygenase (PHM). The cuprous complexes react with O₂ at low temperature generating a reactive copper-oxygen species assigned to a side-on cupric–superoxo complex, which activates the C─H bond of dihydroanthracene. Based on structural, ¹H and ⁷⁷Se NMR, and EPR spectroscopic characterization, together with DFT computations, the selenoether moiety likely acts as a hemilabile ligand in these scaffolds, which results in an electrophilic cupric–superoxide intermediate poised for H-atom transfer, as has been proposed for related bis(benzimidazole)-thioether analogues and selenoether-modified enzymatic systems.

• Author: Brenda N. Sánchez-Eguía; Hugo Hernández-Toledo; Sven Lidin; Marcos Flores-Alamo; Ebbe Nordlander; Sylvain Bertaina; Maylis Orio; Ivan Castillo
• Department/s: Centre for Analysis and Synthesis; NanoLund: Centre for Nanoscience; LTH Profile Area: Nanoscience and Semiconductor Technology; LU Profile Area: Light and Materials; Chemical Physics
• Publishing year: 2025
• Language: English
• Publication/Series: ChemCatChem
• Volume: 17
• Issue: 2
• Links: http://dx.doi.org/10.1002/cctc.202401330
• Document type: Journal article
• Publisher: Wiley-VCH Verlag
• Topic: Organic Chemistry
• Keywords: Copper; C─H activation; DFT calculations; Hemilabile; Monooxygenase
• Status: Published
• ISBN/ISSN/Other: ISSN: 1867-3880