Synthesis and Characterization of a Novel and Recyclable Palladium N-Heterocyclic Carbene Pyrimidine Nanocatalyst on a Periodic Mesoporous Organosilica and Its Performance Investigation in the Suzuki-Miyaura Reaction

Document Type : Research Article


Department of Chemistry, Payame Noor University, PO BOX 19395-3697, Tehran, I.R. IRAN


In this study, N-heterocyclic carbene palladium complex containing pyrimidine supported on a periodic mesoporous organosilica (Pd-Pym-NHC@PMO) was synthesized from 2-aminopyrimidine in four reaction steps. Structure and Physico-chemical properties of Pd-Pym-NHC@PMO was characterized by different techniques of spectroscopic analysis such as XRD, CP-MAS-NMR, AAS, TGA, and BET porosimetry. After full characterization, its catalytic activity in the synthesis of biaryls via the Suzuki–Miyaura cross-coupling was evaluated under the different conditions such as solvent, temperature, and the molar ratio of the reactants. It was observed that the nanocatalyst Pd-Pym-NHC@PMO exhibited excellent activity. Furthermore, the nanocatalyst can be reused and handled at least eight consecutive without any loss of catalytic activity. The present work is a novel, very mild and environmentally friendly method.


Main Subjects

[1] Alente C., OrganM. G., "The Contemporary Suzuki–Miyaura Reaction, in Boronic Acids: Preparation and Applications in Organic Synthesis, Medicine and Materials" (Volume 1 and 2), Second Edition (ed D. G. Hall), Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany (2011).
[2] Miyaura N., Suzuki A., Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds, Chem. Rev., 95 (7): 2457-2483 (1995).
[3] Surry D. S., Buchwald  S. L., Biaryl Phosphine Ligands in Palladium-Catalyzed Amination, Angew. Chem. Int. Ed.,47 (34): 6338-6361(2008).
[4] Surry D. S., Buchwald  S. L., Biarylphosphanliganden in der palladiumkatalysierten Aminierung, Angew. Chem.,120 (34): 6438-6461(2008).
[7]  LennoxaJ. J.,  Lloyd-Jones  G. C., Selection of  Boron Reagents for Suzuki–Miyaura Coupling, Chem. Soc. Rev., 43 (1): 412-443 (2014).
[9] Veerakumar  P., Thanasekaran  P., Lu K.-L., Liu S.-B., Rajagopal S., Functionalized Silica Matrices and Palladium: A Versatile Heterogeneous Catalyst for Suzuki, Heck, and Sonogashira Reactions, ACS Sustainable Chem. Eng., 5 (8): 6357-6376 (2017).
[10] Stratakis M., Garcia H., Catalysis by Supported Gold Nanoparticles: Beyond Aerobic Oxidative Processes, Chem. Rev., 112 (8): 4469-4506 (2012).
[11] Shi J., On the Synergetic Catalytic Effect in Heterogeneous Nanocomposite Catalysts, Chem. Rev., 113 (3): 2139-2181 (2013).
[12] Meyer D., Taige M. A., Zeller A., Hohlfeld K., Ahrens S., Strassner T., Palladium Complexes with Pyrimidine-Functionalized N-Heterocyclic Carbene Ligands: Synthesis, Structure and Catalytic Activity, Organometallics, 28 (7): 2142-2149 (2009).
 [13] Zhao D., Feng J., Huo Q., Melosh N., Fredrickson G. H., Chmelka B. F., Stucky G. D., Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores, Science, 279 (5350): 548-552 (1998).
[14] Kresge C. T., Leonowicz M. E., Roth W. J., Vartuli J. C., Beck J. S., Ordered mesoporous Molecular Sieves Synthesized by a Liquid-Crystal Template Mechanism, Nature, 359 (6397): 710-712 (1992).
[15] AsefaT., MacLachlan M. J., Coombs N., Ozin G. A., Periodic Mesoporous Organosilicas with Organic Groups Inside the Channel Walls, Nature, 402 (6764): 867-871 (1999).
[17] Mohammadi Ziarani G., Aleali F., Lashgari N., Badiei A., An Efficient Green Approach for the Synthesis of Structurally Diversified Spirooxindoles Using Sulfonic Acid Functionalized Nanoporous Silica (SBA-Pr-SO3H), Iran. J. Chem. Chem. Eng., 35 (1): 17-23 (2016).
[18] رشیدی، لادن؛ واشقانی فراهانی، ابراهیم، مروری بر کاربرد نانوذرات مزومتخلخل سیلیکا به عنوان سامانه حمل دارو، نشریه شیمی و مهندسی شیمی ایران، (1)37: 11 تا 49 (1397)
[19] رضوانی، محمدعلی؛ شاطریان، مریم؛ اقمشه، معصومه، گوگردزدایی اکسیداسیونی بنزین با استفاده از نانوکامپوزیت جدید TBA-FePOM@NiO به عنوان یک کاتالیزور موثر و تکرارپذیر، نشریه شیمی و مهندسی شیمی ایران،  (4)37: 77 تا 88 (1397)
[20] Van Der Voort P., Esquivel D., Canck E. D., Goethals F., Driessche I. V., Romero-Salguero F. J., Periodic Mesoporous Organosilicas: from Simple to Complex Bridges; AComprehensive Overview of Functions, Morphologies and Applications, Chem. Soc. Rev., 42(9): 3913-3955 (2013).
[22] Janssen-Müller D., Schlepphorst C., Glorius F., Privileged Chiral N-Heterocyclic Carbene Ligands for Asymmetric Transition-Metal Catalysis, Chem. Soc. Rev.,46 (16): 4845-4854 (2017).
[23] Zhong  R., Lindhorst  A. C., Groche F. J., Kühn F. E., Immobilization of N-Heterocyclic Carbene Compounds: A Synthetic Perspective, Chem. Rev., 117 (3): 1970-2058 (2017).
[24] Meyer D., Strassner T., Methylpalladium Complexes with Pyrimidine-Functionalized N-Heterocyclic Carbene Ligands, Beilstein J. Org. Chem.,12:1557-1565 (2016).