abstract
The catalytic efficiency and selectivity of a series of manganese(III) complexes of meso-tetrakis(pentafluorophenyl)porphyrin H-2(TPFPP) derivatives bearing one to four ethylene glycol moieties are compared in the oxidation of cis-cyclooctene and cyclohexane in the presence of H2O2 at ambient temperature. The results show that the catalysts' performance depends on the number of ethylene glycol moieties present and on the cocatalyst used; for both substrates, the most efficient catalyst in the presence of H2O2 is the Mn(III) complex bearing three ethylene glycol moieties (MnP3). Moreover, in the oxidation of cyclohexane in the presence of iodosylbenzene (PhIO) as oxidant, all the substituted Mn(III) complexes are more efficient than the parent non-substituted Mn(III) porphyrin complex. In addition, during the preparation of this series of derivatives, the tetrasubstituted free-base porphyrin (P4) was further isolated and studied in the solid state, by using single-crystal X-ray diffraction studies. (C) 2016 Elsevier B.V. All rights reserved.
keywords
SOL-GEL PROCESS; HYDROGEN-PEROXIDE; OXIDATION REACTIONS; METALLOPORPHYRIN DERIVATIVES; VERSATILE CATALYSTS; AQUEOUS-SOLUTION; IRON PORPHYRINS; SILICA; HYDROXYLATION; HYDROCARBONS
subject category
Chemistry
authors
Castro, KADF; de Lima, FHC; Simoes, MMQ; Neves, MGPMS; Paz, FAA; Mendes, RF; Nakagaki, S; Cavaleiro, JAS
our authors
Filipe Alexandre Almeida Paz
Principal Researcher
Ricardo Faria Mendes
Junior Researcheracknowledgements
The authors are grateful to Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq), Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES) and Universidade Federal do Parana (UFPR) for financial support. The authors also thank Fundacao para a Ciencia e a Tecnologia (FCT, Portugal), QREN, FEDER and COMPETE founds for the QOPNA (PEst-C/QUI/UI0062/2013; FCOMP-01-0124-FEDER-037296), and Universidade de Aveiro for financial support. Part of this work was developed within the scope of the project 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. Authors further wish to thank CICECO for specific funding towards the purchase of the single crystal X-ray diffractometer. Kelly A.D.F. Castro also thanks CNPq for the granted post-doctoral scholarship (Process: 151512/2013-2 and 201107/2014-7). Ricardo F. Mendes thanks FCT for his PhD scholarship (SFRH/BD/84231/2012).