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Efficient and Reusable Pb(II) Metal–Organic Framework for Knoevenagel Condensation

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Abstract

A microporous lead–organic framework {[Pb4(µ8-MTB)2(H2O)4]·5DMF·H2O}n (MTB = methanetetrabenzoate, DMF = N,N′-dimethylformamide) was synthesized and studied as a catalyst in Knoevenagel condensation reactions. The framework is built from tetranuclear [Pb4(µ3-COO)(µ2-COO)6(COO)(H2O)4] clusters and exhibits a 3D structure, with repeated 1D jar-like cavities with sizes about 14.98 × 7.88 and 14.98 × 13.17 Å2 and BET specific surface area of 980 m2 g−1. To obtain open framework with unsaturated Pb(II) sites needed for catalysis, the thermal activation of the solvent exchanged sample was performed (DMF was exchanged by EtOH). The activated compound was tested in Knoevenagel condensation of bulky aldehydes and active methylene compounds at different temperatures. Excellent catalytic conversion and selectivity in condensation of small-sized aldehydes with malononitrile was observed, which indicates that the opened Pb(II) sites play a significant role in the heterogeneous catalytic process. Leaching test confirmed the stability of the catalyst in catalytic reactions. Moreover, the compound displayed good recyclability after several reuses without significant decrease in the original catalytic activity.

Graphical Abstract

Novel Pb(II) metal–organic framework was tested in Knoevenagel condensation. The catalyst showed excellent catalytic conversion, selectivity and recyclability. Aldehydes with lower kinetic diameter demonstrated high conversions and yields. Catalyst is less efficient for condensation of larger aromatic aldehydes.

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Acknowledgements

This work was supported by the Scientific Grant Agency of the Slovak Republic (VEGA) Project No. 1/0745/17, by the Slovak Research and Development Agency under the contracts APVV-0073-14 and APVV-15-520 and the project from P. J. Šafárik University No. VVGS-2016-249. V.Z. and M.A. thank the Ministry of Education, Science, Research and Sport of the Slovak Republic for the financial support of the TRIANGEL team in the frame of the scheme “Top Research Teams in Slovakia”. J.Č. acknowledges the Czech Science Foundation for the support of the project P106/12/G015.

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Authors and Affiliations

  1. Department of Inorganic Chemistry, Faculty of Science, P. J. Šafárik University, Moyzesova 11, 041 54, Košice, Slovak Republic

    Miroslav Almáši & Vladimír Zeleňák

  2. Department of Synthesis and Catalysis, J. Heyrovský Institute of Physical Chemistry of the ASCR, v.v.i., Academy of Sciences of the Czech Republic, Dolejškova 2155/3, 182 23, Prague 8, Czech Republic

    Maksym V. Opanasenko & Jiří Čejka

Authors
  1. Miroslav Almáši
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  2. Vladimír Zeleňák
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  3. Maksym V. Opanasenko
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  4. Jiří Čejka
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Corresponding author

Correspondence to Vladimír Zeleňák.

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Almáši, M., Zeleňák, V., Opanasenko, M.V. et al. Efficient and Reusable Pb(II) Metal–Organic Framework for Knoevenagel Condensation. Catal Lett 148, 2263–2273 (2018). https://doi.org/10.1007/s10562-018-2471-8

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  • DOI: https://doi.org/10.1007/s10562-018-2471-8

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