{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,26]],"date-time":"2026-03-26T18:39:41Z","timestamp":1774550381628,"version":"3.50.1"},"reference-count":106,"publisher":"MDPI AG","issue":"11","license":[{"start":{"date-parts":[[2022,11,10]],"date-time":"2022-11-10T00:00:00Z","timestamp":1668038400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"Foundation for Science and Technology (FCT), Portugal","doi-asserted-by":"publisher","award":["UIDB\/00100\/2020"],"award-info":[{"award-number":["UIDB\/00100\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"Foundation for Science and Technology (FCT), Portugal","doi-asserted-by":"publisher","award":["UIDP\/00100\/2020"],"award-info":[{"award-number":["UIDP\/00100\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"Foundation for Science and Technology (FCT), Portugal","doi-asserted-by":"publisher","award":["LA\/P\/0056\/2020"],"award-info":[{"award-number":["LA\/P\/0056\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"Foundation for Science and Technology (FCT), Portugal","doi-asserted-by":"publisher","award":["IST-ID\/086\/2018"],"award-info":[{"award-number":["IST-ID\/086\/2018"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"Foundation for Science and Technology (FCT), Portugal","doi-asserted-by":"publisher","award":["IST-ID\/117\/2018"],"award-info":[{"award-number":["IST-ID\/117\/2018"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Catalysts"],"abstract":"<jats:p>The new copper(II) complexes [Cu4(pa)4(Bae)4]\u00b7H2O (1) and [Cu4(eba)4(Buae)4]\u00b7H2O (2) (Hpa = propionic acid, HBae = 2-benzylaminoethanol, Heba = 2-ethylbutyric acid and HBuae = 2-butylaminoethanol) were synthesizsed by the interaction of a copper salt with a methanol solution of the respective ligands. The single-crystal X-ray diffraction analysis reveals that both compounds have a {Cu4(\u03bc3-O)4} cubane-like core. Both compounds show pronounced phenoxazinone synthase-like activity towards the aerobic oxidation of o-aminophenol to phenoxazinone chromophore, with the maximum initial rates W0 up to 3.5 \u00d7 10\u22127 M s\u22121, and exhibit complex non-linear W0 vs. [catalyst]0 dependences. DFT\/\/CCSD theoretical calculations (B3LYP\/ma-def2-TZVP\/\/DLPNO-CCSD(T)\/ma-def2-TZVPP) were employed to investigate the most challenging steps of catalyst-free and copper-catalysed o-aminophenol oxidation (formation of o-aminophenoxyl radical). QTAIM analysis was used to study the key intermediates and weak interactions. Geometries and energies of intermediates and transition states were benchmarked against a series of popular DFT functionals. The results of the calculations demonstrate that a CuII\u2013OO\u2022 copper-superoxo model catalyst decreases the calculated activation barrier from 28.7 to 19.9 kcal mol\u22121 for the catalyst-free and copper-catalysed abstraction of the H atom from the hydroxyl group of o-aminophenol, respectively. Finally, both complexes 1 and 2 were studied as catalysts in the amidation of cyclohexane with benzamide to give N-cyclohexyl benzamide and N-methyl benzamide employing di-tert-butyl peroxide (DTBP) as the oxidant, with a conversion of 16%, and in the oxidation of cyclohexane to cyclohexanol with aq. H2O2, with a conversion of 12%.<\/jats:p>","DOI":"10.3390\/catal12111408","type":"journal-article","created":{"date-parts":[[2022,11,10]],"date-time":"2022-11-10T19:16:23Z","timestamp":1668107783000},"page":"1408","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Tetranuclear Copper Complexes with Bulky Aminoalcohol Ligands as Catalysts for Oxidative Phenoxazinone Synthase-like Coupling of Aminophenol: A Combined Experimental and Theoretical Study"],"prefix":"10.3390","volume":"12","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0114-6525","authenticated-orcid":false,"given":"Oksana V.","family":"Nesterova","sequence":"first","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Institute of Molecular Sciences, Instituto Superior T\u00e9cnico, Universidade de Lisboa, 1049-001 Lisbon, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8323-888X","authenticated-orcid":false,"given":"Armando J. L.","family":"Pombeiro","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Institute of Molecular Sciences, Instituto Superior T\u00e9cnico, Universidade de Lisboa, 1049-001 Lisbon, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1095-6888","authenticated-orcid":false,"given":"Dmytro S.","family":"Nesterov","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Institute of Molecular Sciences, Instituto Superior T\u00e9cnico, Universidade de Lisboa, 1049-001 Lisbon, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2022,11,10]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"5517","DOI":"10.1021\/acs.chemrev.0c00042","article-title":"Activation of Dinitrogen by Polynuclear Metal Complexes","volume":"120","author":"Singh","year":"2020","journal-title":"Chem. 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