A carregar...
Publicação
Bioinspired copper corrole and porphyrin catalysts for oxidation and hydrocarboxylation of alkanes
| Nome: | Descrição: | Tamanho: | Formato: | |
|---|---|---|---|---|
| 2.35 MB | Adobe PDF |
Orientador(es)
Resumo(s)
The development of novel bioinspired catalytic systems that are efficient in the mild oxidative transformation of alkanes remains an attractive research direction in the area of molecular catalysis. In the current study, three copper corrole/porphyrin complexes were synthesized, characterized, and evaluated as homogeneous catalysts in the oxidative transformation of cycloalkanes under mild conditions. New copper complexes of 5,10,15-tris(pentafluorophenyl)corrole and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin derivatives bearing a hydroxyethoxy unit were obtained via the controlled nucleophilic substitution of para fluorine atom with ethylene glycol. The model catalytic processes include: (i) the oxidation of cycloalkanes with H2O2 into a mixture of cyclic ketones and alcohols, and (ii) the hydrocarboxylation of cycloalkanes in the CO/S2O82−/H2O system to generate cycloalkanecarboxylic acids as main products. Both model reactions occur under mild conditions (50−60 °C). Selectivity features, substrate and oxidant scope, and the effects of various reaction parameters were studied and discussed. The best catalysts were the copper corrole derivatives, the performance of which is slightly influenced by the presence of the ethylene glycol moiety. In particular, the copper(III) complex of 5,10,15-tris(pentafluorophenyl)corrole is an efficient catalyst for the mild oxidation and carboxylation of cycloalkanes. This work widens the types of Cu-based corrole/porphyrin derivatives that can be used as bioinspired catalytic systems.
Descrição
Funding Information:
This research work received the support from Fundação para a Ciência e Tecnologia (Portugal), Instituto Superior Técnico, and University of Aveiro. We are grateful to University of Aveiro, Instituto Superior Técnico (CQE-IST, Portugal), and FCT (Fundação para a Ciência e Tecnologia, Portugal) for research facilities and/or funding trough projects: LA/P/0008/2020, UIDP/50006/2020, PTDC/QUI-QIN/3898/2020, UIDB/00100/2020, UIDP/00100/2020, LA/P/0056/2020, UID/00100/2023, and 2022.05950.PTDC. The Portuguese NMR Network and research contracts REF.IST-ID/95/2018 and 2023.08400.CEECIND (C.I.M. Santos), and CEECIND/03708/2017 (M.V. Kirillova) are acknowledged. We thank Dr. T.A. Fernandes and Dr. A.M.M. Antunes for experimental assistance with mass spectrometry studies. We acknowledge the MINDlab: Molecular Design & Innovation Laboratory (MINDlab.pt).
Publisher Copyright:
© 2025 The Author(s)
Palavras-chave
Bioinspired catalysis Copper catalysts Corroles and porphyrins Homogeneous catalysis Oxidation reactions Catalysis Process Chemistry and Technology Physical and Theoretical Chemistry