resumo
In recent years, several research groups have focused their attention on the development of synthetic and functional models of biological systems based on copper. Here we report the synthesis strategy, characterization, and catalytic activity for new copper-based porphyrins (CuP2 and CuP3) isolated by metallation of the corresponding free base derivatives, H(2)P2 and H(2)P3. The solid CuP2S was obtained from the reaction of H2P2 with copper(II) acetate (10 equiv.). These complexes have been used in homogeneous (CuP2 and CuP3) and heterogeneous (CuP2S) oxidative catalysis of 3,5-di-tent-butylcatechol and catechol, in the presence of air, with or without hydrogen peroxide. The obtained results show that the new copper porphyrins CuP2 and CuP3 and the CuP2S material are able to efficiently mimic the activity of catechol oxidase, the latter being easily reused and maintaining its activity for more than three catalytic cycles. (C) 2016 Elsevier Inc. All rights reserved.
palavras-chave
COORDINATION POLYMERS; OXIDATION REACTIONS; METALLOPORPHYRIN DERIVATIVES; CATALYZED OXIDATION; ELECTRONIC-SPECTRA; IRON PORPHYRINS; DNA CLEAVAGE; SOLID-STATE; COMPLEXES; LIGANDS
categoria
Chemistry; Engineering
autores
Castro, KADF; Rodrigues, JMM; Mendes, RF; Neves, MDPMS; Simoes, MMQ; Cavaleiro, JAS; Paz, FAA; Tome, JPC; Nakagaki, S
nossos autores
Filipe Alexandre Almeida Paz
Investigador Principal
João M. M. Rodrigues
Investigador Auxiliar
Ricardo Faria Mendes
Investigador Júnioragradecimentos
We wish to thank the Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq), the Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES), the Fundacao para a Ciencia e a Tecnologia (FCT, Portugal), the European Union, QREN, Fundo Europeu de Desenvolvimento Regional (FEDER) - Portugal through the Programa Operacional Factores de Competitividade (COMPETE), FCT/MEC for financial support to the QOPNA (FCT UID/QUI/00062/2013) and CQE (FCT UID/QUI/0100/2013) research units, through national funds, and where applicable cofinanced by the FEDER, within the PT2020 Partnership Agreement and CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT Ref. UID/CTM/50011/2013), financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. Kelly A.D.F. Castro also thanks CNPq for the post-doctoral scholarship granted (Process: 151512/2013-2 and 201107/2014-7). Ricardo F. Mendes further wishes to thank FCT for Ph.D. scholarship SFRH/BD/84231/2012.