Publication Type Journal Article
Title Environmentally benign benzyl alcohol oxidation and C-C coupling catalysed by amide functionalized 3D Co(II) and Zn(II) metal organic frameworks
Authors A. Paul L.M.D.R.S. Martins Anirban Karmakar Maxim L. Kuznetsov Alexander S. Novikov M. Fátima C. Guedes da Silva Armando J.L. Pombeiro
Groups CCC
Journal JOURNAL OF CATALYSIS
Year 2020
Month May
Volume 385
Number
Pages 324-337
Abstract The new 3D metal-organic frameworks (MOFs) [Co(1 kappa N;2 kappa OO -mu-L)(2)](n).4n(DMF).1.5n(H2O) (1) and [Zn-2(1 kappa N;2 kappa O-mu-L)(2)(kappa O-4-mu(4)-BTC)](n).3n(DmF).2n(H2O) (2) [L = 4-(pyridin-4-ylcarbamoyl)benzoate; BTC = benzene-1,3,5-tricarboxylate] have been synthesized from the pyridyl amide functionalized benzoic acid (HL). They were characterized by elemental, FT-IR, powder X-ray and single crystal X-ray diffraction analyses. Topological analysis of 1 discloses a 2,3,7-connected trinodal net with a 4-connected uninodal net with 2-fold interpenetrating networks, whereas that of 2 shows a dia topology. The solid-state photoluminescent properties of HL and 2 were also investigated. The heterogeneous catalytic activity of 1 and 2, under eco-friendly conditions, was assessed in benzyl alcohol oxidation and C-C bond formation model reactions. 1 has good activity in the solvent-free microwave-assisted oxidation of benzyl alcohol to benzaldehyde using tert-butyl hydroperoxide ((BuOOH)-Bu-t, TBHP) as oxidizing agent (yields up to 89\%). Although with a lower activity, MOF2 with a redox inactive Zn(II) site, also catalyses such alcohol oxidation, which is explained by DFT calculations according to a mechanism of a similar type to that followed by the peroxidative alkane oxidation. 2 is the most active one in the ambient temperature sonochemical Knoevenagel condensation of benzaldehyde and malononitrile (yields up to 94\%) and in the ambient temperature Henry C-C coupling reaction of benzaldehyde with nitroethane in water (yields > 99\%), showing appreciable diastereoselectivity towards the syn isomer. The recyclability of catalysts 1 and 2 was evaluated. (C) 2020 Elsevier Inc. All rights reserved.
DOI http://dx.doi.org/10.1016/j.jcat.2020.03.035
ISBN
Publisher ACADEMIC PRESS INC ELSEVIER SCIENCE
Book Title
ISSN 0021-9517
EISSN 1090-2694
Conference Name
Bibtex ID ISI:000543001200032
Observations
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