Hemilabile Thio– and Selenoethers in Bis(benzimidazolyl)Amine Copper Complexes Relevant to the Active Sites of Copper‐Dependent Monooxygenases
Abstract 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 O 2 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, 1 H and 77 Se 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.
Authors
- Ebbe Nordlander (ORCID: https://orcid.org/0000-0001-9575-4929)
- Hugo Hernández‐Toledo (ORCID: https://orcid.org/0000-0002-6068-4438)
- Brenda N. Sánchez-Eguía (ORCID: https://orcid.org/0000-0002-1535-6662)
- Marcos Flores-Ãlamo (ORCID: https://orcid.org/0000-0002-2996-7616)
- Maylis Orio (ORCID: https://orcid.org/0000-0002-9317-8005)
- Sven Lidin (ORCID: https://orcid.org/0000-0001-9057-8233)
- Iván Castillo (ORCID: https://orcid.org/0000-0002-4876-4339)
- Sylvain Bertaina (ORCID: https://orcid.org/0000-0002-6466-8830)
Institutions
- Centre National de la Recherche Scientifique (FR)
- Lund University (SE)
- Aix-Marseille Université (FR)
- Institut des Matériaux, de Microélectronique et des Nanosciences de Provence (FR)
- Institut des Sciences Moléculaires de Marseille (FR)
- Universidad Nacional Autónoma de México (MX)
Publication Details
- Journal
- ChemCatChem
- Published
- 2024-09-28
- DOI
- https://doi.org/10.1002/cctc.202401330
- Citations
- 3
- Primary Topic
- Metal complexes synthesis and properties
- Type
- article
- Field-Weighted Citation Impact
- 0.85
Funders
- GAVI Alliance
- Consejo Nacional de Ciencia y Tecnología
- Vetenskapsrådet
- Dirección General de Asuntos del Personal Académico, Universidad Nacional Autónoma de México