Environmentally benign benzyl alcohol oxidation and C-C coupling catalysed by amide functionalized 3D Co(II) and Zn(II) metal organic frameworks

Anup Paul, Luísa M.D.R.S. Martins, Anirban Karmakar, Maxim L. Kuznetsov, Alexander S. Novikov, M. Fátima C. Guedes da Silva, Armando J.L. Pombeiro

Результат исследований: Научные публикации в периодических изданияхстатья

2 Цитирования (Scopus)

Аннотация

The new 3D metal-organic frameworks (MOFs) [Co(1κN;2κOO′-μ-L)2]n.4n(DMF).1.5n(H2O) (1) and [Zn2(1κN;2κO-μ-L)2(κO44-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 (tBuOOH, TBHP) as oxidizing agent (yields up to 89%). Although with a lower activity, MOF 2 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.

Язык оригиналаанглийский
Страницы (с-по)324-337
Число страниц14
ЖурналJournal of Catalysis
Том385
DOI
СостояниеОпубликовано - мая 2020

Предметные области Scopus

  • Катализ
  • Физическая и теоретическая химия

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