ACS Publications. Most Trusted. Most Cited. Most Read
Metal Azolate/Carboxylate Frameworks as Catalysts in Oxidative and C–C Coupling Reactions

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2016, 55, 12, 5804-5817
    Article

    Metal Azolate/Carboxylate Frameworks as Catalysts in Oxidative and C–C Coupling Reactions
    Click to copy article linkArticle link copied!

    View Author Information
    † Department of Chemistry, Physics and Environment, Faculty of Sciences and Environment, “Dunarea de Jos” University of Galati, 111 Domneasca Street, 800201 Galati, Romania
    ‡ School of Pharmacy, Chemistry Section, University of Camerino, Via S. Agostino 1, 62032 Camerino, Italy
    § Chemical Engineering Department, Instituto Superior de Engenharia de Lisboa, Instituto Politécnico de Lisboa, R. Conselheiro Emídio Navarro, 1959-007 Lisboa, Portugal
    ∥ Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Avenida Rovisco Pais, 1049-001 Lisboa, Portugal
    ⊥ Dipartimento di Scienza e Alta Tecnologia, Università dell’Insubria, Via Valleggio 11, 22100 Como, Italy
    # ID22 High-Resolution Powder-Diffraction Beamline, European Synchrotron Radiation Facility, CS 40220, 38043 Grenoble Cedex 9, France
    National Taras Shevchenko University of Kyiv, Volodimirska Strasse 64, 01033 Kyiv, Ukraine
    *E-mail: [email protected]
    *E-mail: [email protected]
    *E-mail: [email protected]
    *E-mail: [email protected]
    Other Access OptionsSupporting Information (2)

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2016, 55, 12, 5804–5817
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.5b02997
    Published June 6, 2016
    Copyright © 2016 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    The five metal azolate/carboxylate (MAC) compounds [Cd(dmpzc)(DMF)(H2O)] (Cd-dmpzc), [Pd(H2dmpzc)2Cl2] (Pd-dmpzc), [Cu(Hdmpzc)2] (Cu-dmpzc), [Zn4O(dmpzc)3]·Solv (Zn-dmpzc·S), and [Co4O(dmpzc)3]·Solv (Co-dmpzc·S) were isolated by coupling 3,5-dimethyl-1H-pyrazol-4-carboxylic acid (H2dmpzc) to cadmium(II), palladium(II), copper(II), zinc(II), and cobalt(II) salts. While Cd-dmpzc and Pd-dmpzc had never been prepared in the past, for Cu-dmpzc, Zn-dmpzc·S, and Co-dmpzc·S we optimized alternative synthetic paths that, in the case of the copper(II) and cobalt(II) derivatives, are faster and grant higher yields than the previously reported ones. The crystal structure details were determined ab initio (Cd-dmpzc and Pd-dmpzc) or refined (Cu-dmpzc, Zn-dmpzc·S, and Co-dmpzc·S) by means of powder X-ray diffraction (PXRD). While Cd-dmpzc is a nonporous 3D MAC framework, Pd-dmpzc shows a 3D hybrid coordination/hydrogen-bonded network, in which Pd(H2dmpzc)2Cl2 monomers are present. The thermal behavior of the five MAC compounds was investigated by coupling thermal analysis to variable-temperature PXRD. Their catalytic activity was assessed in oxidative and C–C coupling reactions, with the copper(II) and cadmium(II) derivatives being the first nonporous MAC frameworks to be tested as catalysts. Cu-dmpzc is the most active catalyst in the partial oxidation of cyclohexane by tert-butyl hydroperoxide in acetonitrile (yields up to 12% after 9 h) and is remarkably active in the solvent-free microwave-assisted oxidation of 1-phenylethanol to acetophenone (yields up to 99% at 120 °C in only 0.5 h). On the other hand, activated Zn-dmpzc·S (Zn-dmpzc) is the most active catalyst in the Henry C–C coupling reaction of aromatic aldehydes with nitroethane, showing appreciable diastereoselectivity toward the syn-nitroalkanol isomer (syn:anti selectivity up to 79:21).

    Copyright © 2016 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.5b02997.

    • X-ray crystallographic data in CIF format (CIF)

    • Crystal X-ray analysis, IR spectroscopy, thermal behavior, and catalytic activity (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 21 publications.

    1. Cheng-Peng Zhang, Yu-Jun Zhu, Danfeng Wang, Junfeng Qian, Yu-Pei Zhao, Cheng Lian, Zhi-Hui Zhang, Ming-Yang He, Sheng-Chun Chen, Qun Chen. Ligand-Mediated Regulation of the Chemical/Thermal Stability and Catalytic Performance of Isostructural Cobalt(II) Coordination Polymers. Inorganic Chemistry 2023, 62 (43) , 17678-17690. https://doi.org/10.1021/acs.inorgchem.3c02184
    2. Marzena Fandzloch, Weronika Bodylska, Joanna Trzcińska-Wencel, Patrycja Golińska, Katarzyna Roszek, Joanna Wiśniewska, Michał Bartmański, Agnieszka Lewińska, Anna Jaromin. Cu-HKUST-1 and Hydroxyapatite–The Interface of Two Worlds toward the Design of Functional Materials Dedicated to Bone Tissue Regeneration. ACS Biomaterials Science & Engineering 2023, 9 (8) , 4646-4653. https://doi.org/10.1021/acsbiomaterials.3c00594
    3. Bharat Ugale, Sandeep Kumar, T. J. Dhilip Kumar, C. M. Nagaraja. Environmentally Friendly, Co-catalyst-Free Chemical Fixation of CO2 at Mild Conditions Using Dual-Walled Nitrogen-Rich Three-Dimensional Porous Metal–Organic Frameworks. Inorganic Chemistry 2019, 58 (6) , 3925-3936. https://doi.org/10.1021/acs.inorgchem.8b03612
    4. Alexey N. Bilyachenko, Alena N. Kulakova, Mikhail M. Levitsky, Artem A. Petrov, Alexander A. Korlyukov, Lidia S. Shul’pina, Victor N. Khrustalev, Pavel V. Dorovatovskii, Anna V. Vologzhanina, Ulyana S. Tsareva, Igor E. Golub, Ekaterina S. Gulyaeva, Elena S. Shubina, and Georgiy B. Shul’pin . Unusual Tri-, Hexa-, and Nonanuclear Cu(II) Cage Methylsilsesquioxanes: Synthesis, Structures, and Catalytic Activity in Oxidations with Peroxides. Inorganic Chemistry 2017, 56 (7) , 4093-4103. https://doi.org/10.1021/acs.inorgchem.7b00061
    5. Anna Brodzka, Dominik Koszelewski, Anna Trzeciak, Lena Ruzik, Malgorzata Grela, Ryszard Ostaszewski. The Influence of Ligands on the Pd-Catalyzed Diarylation of Vinyl Esters. Molecules 2024, 29 (10) , 2268. https://doi.org/10.3390/molecules29102268
    6. John R. Kromer, Alan J. Oberley, Lava R. Kadel, Derek Vonarx, Jared McNeil, Joan Haskin, Ryan M. Steinert, Katie R. Mitchell-Koch, Curtis E. Moore, David M. Eichhorn. Synthesis and X-ray crystal structures of mononuclear and multinuclear metal complexes of 3-substituted 4-cyanopyrazole ligands. Polyhedron 2023, 243 , 116546. https://doi.org/10.1016/j.poly.2023.116546
    7. Nertil Xhaferaj, Aurel Tăbăcaru, Claudio Pettinari, Kostiantyn V. Domasevitch, Simona Galli. Synthesis and structural characterization of metal azolate/carboxylate frameworks incorporating the 1-H-pyrazol-3,4,5-tricarboxylate ligand. Inorganica Chimica Acta 2023, 544 , 121236. https://doi.org/10.1016/j.ica.2022.121236
    8. Waleed Alsalahi, Adam W. Augustyniak, Włodzimierz Tylus, Anna M. Trzeciak. New Palladium – ZrO 2 Nano‐Architectures from Thermal Transformation of UiO‐66‐NH 2 for Carbonylative Suzuki and Hydrogenation Reactions. Chemistry – A European Journal 2022, 28 (6) https://doi.org/10.1002/chem.202103538
    9. Adam W. Augustyniak, Anna M. Trzeciak. Phenylacetylene semihydrogenation over a palladium pyrazolate hydrogen-bonded network. Inorganica Chimica Acta 2021, 518 , 120255. https://doi.org/10.1016/j.ica.2021.120255
    10. Y. Boncli. metal azolate framework. 2020https://doi.org/10.1002/9783527809080.cataz10459
    11. Telma F. S. Silva, Luísa M. D. R. S. Martins. Recent Advances in Copper Catalyzed Alcohol Oxidation in Homogeneous Medium. Molecules 2020, 25 (3) , 748. https://doi.org/10.3390/molecules25030748
    12. Sima Aryanejad, Ghodsieh Bagherzade, Maryam Moudi. Design and development of novel Co‐MOF nanostructures as an excellent catalyst for alcohol oxidation and Henry reaction, with a potential antibacterial activity. Applied Organometallic Chemistry 2019, 33 (6) https://doi.org/10.1002/aoc.4820
    13. Manas Sutradhar, Luísa M. D. R. S. Martins, M. Fátima C. Guedes da Silva,, Armando J. L. Pombeiro. Alkane Oxidation with Vanadium and Copper Catalysts. 2019, 319-336. https://doi.org/10.1002/9781119379256.ch16
    14. Maxim L. Kuznetsov. Nontransition Metal Catalyzed Oxidation of Alkanes with Peroxides. 2019, 485-501. https://doi.org/10.1002/9781119379256.ch22
    15. Roozbeh Javad Kalbasi, Sanaz Mansouri, Omid Mazaheri. In situ polymerization of poly(vinylimidazole) into the pores of ‎hierarchical MFI zeolite as an acid–base bifunctional catalyst for one-pot ‎C–C bond cascade reactions. Research on Chemical Intermediates 2018, 44 (5) , 3279-3291. https://doi.org/10.1007/s11164-018-3306-3
    16. Francisco G. Cirujano, Elena López‐Maya, Marleny Rodríguez‐Albelo, Elisa Barea, Jorge A. R. Navarro, Dirk E. De Vos. Selective One‐Pot Two‐Step C−C Bond Formation using Metal–Organic Frameworks with Mild Basicity as Heterogeneous Catalysts. ChemCatChem 2017, 9 (21) , 4019-4023. https://doi.org/10.1002/cctc.201700784
    17. Nuno Martins, Luísa Martins, Carlos Amorim, Vitor Amaral, Armando Pombeiro. First-Row-Transition Ion Metals(II)-EDTA Functionalized Magnetic Nanoparticles as Catalysts for Solvent-Free Microwave-Induced Oxidation of Alcohols. Catalysts 2017, 7 (11) , 335. https://doi.org/10.3390/catal7110335
    18. Salim Saranya, Nissy Ann Harry, Sankuviruthiyil M. Ujwaldev, Gopinathan Anilkumar. Recent Advances and Perspectives on the Zinc‐Catalyzed Nitroaldol (Henry) Reaction. Asian Journal of Organic Chemistry 2017, 6 (10) , 1349-1360. https://doi.org/10.1002/ajoc.201700290
    19. Valentina Colombo, Alessandro Cimino, Angelo Maspero, Stefano Tollari, Giovanni Palmisano, Angelo Sironi. Cu(II) bifunctional (N,O,O′) coordination polymer: A case study for complex ab-initio crystal structure determination from PXRD data. Solid State Sciences 2017, 71 , 22-28. https://doi.org/10.1016/j.solidstatesciences.2017.06.015
    20. Raja Jlassi, Ana P.C. Ribeiro, Marta Mendes, Walid Rekik, Gonçalo A.O. Tiago, Kamran T. Mahmudov, Houcine Naïli, M. Fátima C. Guedes da Silva, Armando J.L. Pombeiro. Arylhydrazone Cd(II) and Cu(II) complexes as catalysts for secondary alcohol oxidation. Polyhedron 2017, 129 , 182-188. https://doi.org/10.1016/j.poly.2017.03.020
    21. Smaail Radi, Mohamed El-Massaoudi, Houria Benaissa, N. N. Adarsh, Marilena Ferbinteanu, Eamonn Devlin, Yiannis Sanakis, Yann Garcia. Crystal engineering of a series of complexes and coordination polymers based on pyrazole-carboxylic acid ligands. New Journal of Chemistry 2017, 41 (16) , 8232-8241. https://doi.org/10.1039/C7NJ01714F
    Download PDF
    Go to Inorganic Chemistry
    Get e-Alerts
    Get e-Alerts

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2016, 55, 12, 5804–5817
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.5b02997
    Published June 6, 2016
    Copyright © 2016 American Chemical Society
    Request reuse permissions

    Article Views

    1488

    Altmetric

    -

    Citations

    21
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.