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Phenoxazinone synthase-like catalytic activity of bi- and trinuclear copper(II) complexes with 2- benzylethanolamine: experimental and theoretical investigations

2025-05Artigo de investigação Acesso aberto
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authorProfile.emailbiblioteca@isel.pt
datacite.subject.fosEngenharia e Tecnologia::Engenharia Química
dc.contributor.authorNesterova, Oksana V.
dc.contributor.authorBondarenko, Olena E.
dc.contributor.authorPombeiro, Armando
dc.contributor.authorNesterov, Dmytro S.
dc.date.accessioned2026-02-18T09:39:13Z
dc.date.available2026-02-18T09:39:13Z
dc.date.issued2025-05
dc.descriptionThis work was supported by the Fundação para a Ciência e a Tecnologia, I.P/; MCTES through national funds PIDDAC – CQE UIDB/00100/2020 and UIDP/00100/2020 (DOI 10.54499/UIDP/00100/2020) and IMS the Associated Laboratory funded by Project LA/P/0056/2020 (DOI 10.54499/LA/P/0056/2020). The simulations reported in this paper were in part performed at the OBLIVION Supercomputer (HPC Centre of the University of Évora, Portugal) of the “Enabling Green E-science for the SKA Research Infrastructure (ENGAGE SKA)”, reference POCI-01–0145-FEDER-022217, funded by COMPETE 2020 and Foundation for Science and Technology (FCT), Portugal. This research was funded by the FCT under project 2023.10683.CPCA.A1.
dc.description.abstractAbstract The self-assembly reaction of 2-benzylaminoethanol (Hbae) with CuCl2 or Cu(NO3)2 leads to the formation of binuclear [Cu2(bae)2(Cl)2] (1) and [Cu2(Hbae)2(bae)2](NO3)2 (2) complexes, while the trinuclear [Cu3(Hbae)2(bae)2(dmba)2](NO3)2 (3) compound was obtained using the auxiliar bulky substituted 2,2-dimethylbutyric acid (Hdmba). Crystallographic studies reveal the molecular structures of 1 and 2 based on the similar {Cu2(μ-O)2} core, while the structure of 3 features the {Cu3(μ-O)2} core with consecutive arranement of the metal centres, supported by the additional carboxylate bridges. The strong intermolecular hydrogen bonds join the molecular structures into 1D (for 1 and 3) or 2D (for 2) architectures. All three compounds act as catalysts for the aerobic oxidation of 2-aminophenol to the phenoxazinone chromophore (phenoxazinone synthase-like activity) with the maximum reaction rates up to 2.3×10-8 M s-1. The substrate scope involves methyl-, nitro- and chloro-substituted 2-aminophenols, disclosing the negligible activity of nitro-derivatives, while the 6-amino-m-cresol substrate shows the highest activity with the initial reaction rate of 5.8×10-8 M s-1. The mechanism of the rate-limiting reaction step (copper-catalysed formation of 2-aminophenoxyl radicals) was investigated at the DFT level. The combined DFT and CASSCF studies of the copper superoxo CuII-OO⋅ radical species as possible unconventional reaction intermediates resulted in a rational mechanism of H-atom abstraction, where the activation energies follow the experimental reactivity of substituted 2-aminophenols. The TDDFT and STEOM-DLPNO-CCSD theoretical calculations of the absorption spectra of substrates, phenoxazinone chromophores and putative polynuclear species containing 2-aminophenoxo ligand are reported.eng
dc.identifier.citationNesterova, O. V., Bondarenko, O. E., Pombeiro, A. J. L., & Nesterov, D. S. (2025). Phenoxazinone synthase-like catalytic activity of bi- and trinuclear copper(II) complexes with 2- benzylethanolamine: experimental and theoretical investigations. ChemPlusChem, 90(5), e202400613. https://10.1002/cplu.202400613
dc.identifier.doi10.1002/cplu.202400613
dc.identifier.eissn2192-6506
dc.identifier.issn2192-6506
dc.identifier.urihttp://hdl.handle.net/10400.21/22664
dc.language.isoeng
dc.peerreviewedyes
dc.publisherWiley-VCH GmbH
dc.relationCentro de Química Estrutural
dc.relationLA/P/0056/2020
dc.relation.hasversionhttps://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/cplu.202400613
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subjectAminophenol
dc.subjectCopper
dc.subjectCopper superoxol compounds
dc.subjectDFT theoretical calculations of reaction mechanism
dc.subjectPhenoxazinone synthase-like catalysis
dc.subjectUIDB/00100/2020
dc.subjectUIDP/00100/2020
dc.subjectLA/P/0056/2020
dc.titlePhenoxazinone synthase-like catalytic activity of bi- and trinuclear copper(II) complexes with 2- benzylethanolamine: experimental and theoretical investigationseng
dc.typeresearch article
dspace.entity.typePublication
oaire.awardTitleCentro de Química Estrutural
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F00100%2F2020/PT
oaire.citation.endPage15
oaire.citation.issue5
oaire.citation.startPage1
oaire.citation.titleChemPlusChem
oaire.citation.volume90
oaire.fundingStream6817 - DCRRNI ID
oaire.versionhttp://purl.org/coar/version/c_be7fb7dd8ff6fe43
person.familyNamePombeiro
person.givenNameArmando
person.identifier.ciencia-id8311-38FA-CEFB
person.identifier.orcid0000-0001-8323-888X
person.identifier.ridI-5945-2012
person.identifier.scopus-author-id7006067269
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.nameFundação para a Ciência e a Tecnologia
relation.isAuthorOfPublication6d18ff2e-5c33-4010-b1e7-964c72349813
relation.isAuthorOfPublication.latestForDiscovery6d18ff2e-5c33-4010-b1e7-964c72349813
relation.isProjectOfPublication4ca2f791-5aae-48f8-ac70-bde2e34d442a
relation.isProjectOfPublication.latestForDiscovery4ca2f791-5aae-48f8-ac70-bde2e34d442a

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