Back to Search
Start Over
Orbital Analysis Captures the Existence of a Mixed-Valent Cu III -O-Cu II Active-Site and its Role in Water-Assisted Aliphatic Hydroxylation.
- Source :
-
Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Mar 07; Vol. 30 (14), pp. e202303722. Date of Electronic Publication: 2024 Jan 18. - Publication Year :
- 2024
-
Abstract
- The Cu-O-Cu core has been proposed as a potential site for methane oxidation in particulate methane monooxygenase. In this work, we used density functional theory (DFT) to design a mixed-valent Cu <superscript>III</superscript> -O-Cu <superscript>II</superscript> species from an experimentally known peroxo-dicopper complex supported by N-donor ligands containing phenolic groups. We found that the transfer of two-protons and two-electrons from phenolic groups to peroxo-dicopper core takes place, which results to the formation of a bis-μ-hydroxo-dicopper core. The bis-μ-hydroxo-dicopper core converts to a mixed-valent Cu <superscript>III</superscript> -O-Cu <superscript>II</superscript> core with the removal of a water molecule. The orbital and spin density analyses unravel the mixed-valent nature of Cu <superscript>III</superscript> -O-Cu <superscript>II</superscript> . We further investigated the reactivity of this mixed-valent core for aliphatic C-H hydroxylation. Our study unveiled that mixed-valent Cu <superscript>III</superscript> -O-Cu <superscript>II</superscript> core follows a hydrogen atom transfer mechanism for C-H activation. An in-situ generated water molecule plays an important role in C-H hydroxylation by acting as a proton transfer bridge between carbon and oxygen. Furthermore, to assess the relevance of a mixed-valent Cu <superscript>III</superscript> -O-Cu <superscript>II</superscript> core, we investigated aliphatic C-H activation by a symmetrical Cu <superscript>II</superscript> -O-Cu <superscript>II</superscript> core. DFT results show that the mixed-valent Cu <superscript>III</superscript> -O-Cu <superscript>II</superscript> core is more reactive toward the C-H bond than the symmetrical Cu <superscript>II</superscript> -O-Cu <superscript>II</superscript> core.<br /> (© 2024 Wiley-VCH GmbH.)
Details
- Language :
- English
- ISSN :
- 1521-3765
- Volume :
- 30
- Issue :
- 14
- Database :
- MEDLINE
- Journal :
- Chemistry (Weinheim an der Bergstrasse, Germany)
- Publication Type :
- Academic Journal
- Accession number :
- 38168869
- Full Text :
- https://doi.org/10.1002/chem.202303722