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

Sánchez-Eguía, Brenda N. ; Hernández-Toledo, Hugo LU ; Lidin, Sven LU ; Flores-Alamo, Marcos ; Nordlander, Ebbe LU ; Bertaina, Sylvain ; Orio, Maylis and Castillo, Ivan (2024) In ChemCatChem
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 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... (More)

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.

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author
; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
epub
subject
keywords
Copper, C─H activation, DFT calculations, Hemilabile, Monooxygenase
in
ChemCatChem
publisher
John Wiley & Sons Inc.
external identifiers
  • scopus:85205875292
ISSN
1867-3880
DOI
10.1002/cctc.202401330
language
English
LU publication?
yes
id
47093f41-ae2f-4ef2-9cdb-7c232f4290a4
date added to LUP
2024-12-18 15:25:38
date last changed
2024-12-18 15:26:30
@article{47093f41-ae2f-4ef2-9cdb-7c232f4290a4,
  abstract     = {{<p>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<sub>2</sub> 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, <sup>1</sup>H and <sup>77</sup>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.</p>}},
  author       = {{Sánchez-Eguía, Brenda N. and Hernández-Toledo, Hugo and Lidin, Sven and Flores-Alamo, Marcos and Nordlander, Ebbe and Bertaina, Sylvain and Orio, Maylis and Castillo, Ivan}},
  issn         = {{1867-3880}},
  keywords     = {{Copper; C─H activation; DFT calculations; Hemilabile; Monooxygenase}},
  language     = {{eng}},
  publisher    = {{John Wiley & Sons Inc.}},
  series       = {{ChemCatChem}},
  title        = {{Hemilabile Thio– and Selenoethers in Bis(benzimidazolyl)Amine Copper Complexes Relevant to the Active Sites of Copper-Dependent Monooxygenases}},
  url          = {{http://dx.doi.org/10.1002/cctc.202401330}},
  doi          = {{10.1002/cctc.202401330}},
  year         = {{2024}},
}