Abstract
In the present work, we invented a Pd nanoparticle immobilized on an amine-functionalized LDH catalyst (PdNP@NH2-LDH-Al-MCM-41) for cross-coupling reactions. The palladium was grafted onto the support by treating the Pd(OAc)2 with NH2-LDH-Al-MCM-41 in acetone at room temperature. The prepared catalyst was characterized by FT-IR, SEM, TGA, TEM, and XPS techniques. The TEM characterization of the catalyst showed the uniform distribution of PdNPs with sizes ranging from 3 to 6 nm located inside the mesoporous. The Suzuki–Miyaura cross-coupling reaction was used to demonstrate the catalytic efficiency of the prepared PdNPs@NH2-LDH-Al-MCM-41 catalyst. The prepared and analyzed catalyst showed good to excellent activity in the Suzuki–Miyaura cross-coupling reaction of various aryl bromides with different aryl boronic acids in ethanol at 80 °C. The catalyst showed TON up to ~ 47 and TOF ~ 47 h−1. The catalytic results exhibited that the catalyst is completely recoverable with simple filtration. The catalytic efficiency shows a slight decrease in activity for the Suzuki–Miyaura cross-coupling reactions even after five repeated recycles. TEM images of the freshly prepared and reused catalysts (after five catalytic cycles) showed palladium nanoparticles remain unchanged at the end of the reactions.
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Balanta A, Godard C, Claver C (2011) Pd nanoparticles for C-C coupling reactions. Chem Soc Rev 40(10):4973–4985. https://doi.org/10.1039/C1CS15195A
Bérend I, Cases J-M, François M, Uriot J-P, Michot L, Masion A, Thomas F (1995) Mechanism of adsorption and desorption of water vapor by homoionic montmorillonites: 2. The Li+ Na+, K+, Rb+ and Cs+-exchanged forms. Clays Clay Miner 43(3):324–336. https://doi.org/10.1346/CCMN.1995.0430307
Braga AAC, Morgon NH, Ujaque G, Maseras F (2005) Computational characterization of the role of the base in the Suzuki−Miyaura cross-coupling reaction. J Am Chem Soc 127(25):9298–9307. https://doi.org/10.1021/ja050583i
Brase S, deMeijere A, Diederich F SP (1998) Metal-catalyzed cross-coupling reactions
Cauvel A, Renard G, Brunel D (1997) Monoglyceride synthesis by heterogeneous catalysis using MCM-41 Type silicas functionalized with amino groups. J Org Chem 62(3):749–751. https://doi.org/10.1021/jo9614001
Chatterjee S, Bhattacharya SK (2018) Size-dependent catalytic activity and fate of palladium nanoparticles in Suzuki-Miyaura coupling reactions. ACS Omega 3(10):12905–12913. https://doi.org/10.1021/acsomega.8b01598
Chen C-Y, Li H-X, Davis ME (1993) Studies on mesoporous materials: I. Synthesis and characterization of MCM-41. Microporous Mater 2(1):17–26. https://doi.org/10.1016/0927-6513(93)80058-3
Cherney AH, Kadunce NT, Reisman SE (2015) Enantioselective and enantiospecific transition-metal-catalyzed cross-coupling reactions of organometallic reagents to construct C-C bonds. Chem Rev 115(17):9587–9652. https://doi.org/10.1021/acs.chemrev.5b00162
Choudary BM, Madhi S, Chowdari NS, Kantam ML, Sreedhar B (2002) Layered double hydroxide supported nanopalladium catalyst for Heck-, Suzuki-, Sonogashira-, and Stille-type coupling reactions of chloroarenes. J Am Chem Soc 124(47):14127–14136. https://doi.org/10.1021/ja026975w
Das P, Prabhakaran VC, Nanda S, Sen D, Chowdhury B (2019) Palladium impregnated amine co-condensed hexagonal mesoporous silica: a novel catalyst in tailoring Suzuki and Heck coupling reactions in base free condition. Chem Select 4:3823–3832. https://doi.org/10.1002/slct.201803485
de Meijere A, Bräse S, Oestreich M (2013) Metal catalyzed cross-coupling reactions and more. 3:1–1511. Doi: https://doi.org/10.1002/9783527655588
Del Zotto A, Zuccaccia D (2017) Metallic palladium{,} PdO{,} and palladium supported on metal oxides for the Suzuki-Miyaura cross-coupling reaction: a unified view of the process of formation of the catalytically active species in solution. Catal Sci Technol 7(18):3934–3951. https://doi.org/10.1039/C7CY01201B
Díaz-Sánchez M, Díaz-García D, Prashar S, Gómez-Ruiz S (2019) Palladium nanoparticles supported on silica, alumina or Titania: greener alternatives for Suzuki-Miyaura and other C-C coupling reactions. Environ Chem Lett 17:1585–1602. https://doi.org/10.1007/s10311-019-00899-5
Díaz-Sánchez M, Gómez I, Prashar S, Horáček M, Lamač M, Urbán B, Pinkas J, Gómez-Ruiz S (2021) Multifunctional catalysts based on palladium nanoparticles supported on functionalized halloysites: applications in catalytic C-C coupling, selective oxidation and dehalogenation reactions. Appl Clay Sci 214(15):106272. https://doi.org/10.1016/j.clay.2021.106272
Fan G, Li F, Evans DG, Duan X (2014) Catalytic applications of layered double hydroxides: recent advances and perspectives. Chem Soc Rev 43(20):7040–7066. https://doi.org/10.1039/C4CS00160E
Fu L, Huo C, He X, Yang H (2015) Au encapsulated into Al-MCM-41 mesoporous material: in situ synthesis and electronic structure. RSC Adv 5(26):20414–20423. https://doi.org/10.1039/C5RA01701G
Fukaya N, Ueda M, Onozawa S, Bando KK, Miyaji T, Takagi Y, Sakakura T, Yasuda H (2011) Palladium complex catalysts immobilized on silica via a tripodal linker unit with amino groups: Preparation, characterization, and application to the Suzuki-Miyaura coupling. J Mol Catal A Chem 342–343:58–66. https://doi.org/10.1016/j.molcata.2011.04.012
Heravi MM, Mohammadi P (2022) Layered double hydroxides as heterogeneous catalyst systems in the cross-coupling reactions: an overview. Mol Divers 26(1):569–587. https://doi.org/10.1007/s11030-020-10170-7
Hong J, Zaera F (2012) Interference of the surface of the solid on the performance of tethered molecular catalysts. J Am Chem Soc 134(31):13056–13065. https://doi.org/10.1021/ja304181q
Hong K, Sajjadi M, Suh JM, Zhang K, Nasrollahzadeh M, Jang HW, Varma RS, Shokouhimehr M (2020) Palladium nanoparticles on assorted nanostructured supports: applications for Suzuki, Heck, and Sonogashira cross-coupling reactions. ACS Appl Nano Mater 3(3):2070–2103. https://doi.org/10.1021/acsanm.9b02017
Jadhav SN, Rode CV (2017) An efficient palladium-catalyzed Mizoroki-Heck cross-coupling in water. Green Chem 19(24):5958–5970. https://doi.org/10.1039/C7GC02869E
Jadhav S, Kumbhar A, Salunkhe R (2015) Palladium supported on silica–chitosan hybrid material (Pd-CS@SiO2) for Suzuki-Miyaura and Mizoroki-Heck cross-coupling reactions. Appl Organomet Chem 29(6):339–345. https://doi.org/10.1002/aoc.3290
Jadhav SN, Kumbhar AS, Mali SS, Hong CK, Salunkhe RS (2015b) A Merrifield resin supported Pd–NHC complex with a spacer(Pd–NHC@SP–PS) for the Sonogashira coupling reaction under copper- and solvent-free conditions. New J Chem 39(3):2333–2341. https://doi.org/10.1039/C4NJ02025A
Jadhav SN, Kumbhar AS, Rode CV, Salunkhe RS (2016) Ligand-free Pd catalyzed cross-coupling reactions in an aqueous hydrotropic medium. Green Chem 18(7):1898–1911. https://doi.org/10.1039/C5GC02314A
Jeffery T, Liebeskind L (1996) Advances in metal-organic chemistry. Jai Press, Greenwich
Kambe N, Iwasaki T, Terao J (2011) Pd-catalyzed cross-coupling reactions of alkyl halides. Chem Soc Rev 40(10):4937–4947. https://doi.org/10.1039/C1CS15129K
Karimi B, Khorasani M, Vali H, Vargas C, Luque R (2015) Palladium nanoparticles supported in the nanospaces of imidazolium-based bifunctional PMOs: the role of plugs in selectivity changeover in aerobic oxidation of alcohols. ACS Catal 5(7):4189–4200. https://doi.org/10.1021/acscatal.5b00237
Khalili D, Banazadeh AR, Etemadi-Davan E (2017) Palladium stabilized by amino-vinyl silica functionalized magnetic carbon nanotube: application in Suzuki-Miyaura and Heck-Mizoroki coupling reactions. Catal Lett 147:2674–2687. https://doi.org/10.1007/s10562-017-2150-1
Khan M, Shaik MR, Adil SF, Kuniyil M, Ashraf M, Frerichs H, Sarif MA, Siddiqui MRH, Al–Warthan A, Labis JP, Islam MS, Tremel W, Tahir MN (2020) Facile synthesis of Pd@graphene nanocomposites with enhanced catalytic activity towards Suzuki coupling reaction. Sci Rep 10(1):11728. https://doi.org/10.1038/s41598-020-68124-w
King AO, Yasuda N (2004) Palladium-catalyzed cross-coupling reactions in the synthesis of pharmaceuticals. Organometallics in process chemistry. Springer, Berlin, pp 205–245
Kumbhar A (2017) Functionalized nitrogen ligands for palladium catalyzed cross-coupling reactions (part I). J Organomet Chem 848:22–88. https://doi.org/10.1016/j.jorganchem.2017.07.009
Kumbhar A (2019) Functionalized nitrogen ligands (CN) for palladium catalyzed cross-coupling reactions (part II). J Organomet Chem 881:79–129. https://doi.org/10.1016/j.jorganchem.2018.09.020
Kumbhar A, Jadhav S, Kamble S, Rashinkar G, Salunkhe R (2013) Palladium supported hybrid cellulose–aluminum oxide composite for Suzuki-Miyaura cross coupling reaction. Tetrahedron Lett 54(11):1331–1337. https://doi.org/10.1016/j.tetlet.2012.11.140
Kumbhar A, Kamble S, Mane A, Jha R, Salunkhe R (2013) Modified zeolite immobilized palladium for ligand-free Suzuki-Miyaura cross-coupling reaction. J Organomet Chem 738:29–34. https://doi.org/10.1016/j.jorganchem.2013.03.031
Lee DH, Jung JY, Jin MJ (2010) Highly active and recyclable silica gel-supported palladium catalyst for mild cross-coupling reactions of unactivated heteroaryl chlorides. Green Chem 12:2024–2029. https://doi.org/10.1039/C0GC00251H
Li C-J (2005) Organic reactions in aqueous media with a focus on carbon−carbon bond formations: a decade update. Chem Rev 105(8):3095–3166. https://doi.org/10.1021/cr030009u
Liu L, Corma A (2018) Metal catalysts for heterogeneous catalysis: from single atoms to nanoclusters and nanoparticles. Chem Rev 118(10):4981–5079. https://doi.org/10.1021/acs.chemrev.7b00776
Liu J, Hao J, Hu C, He B, Xi J, Xiao J, Wang S, Bai Z (2018) Palladium nanoparticles anchored on amine-functionalized silica nanotubes as a highly effective catalyst. J Phys Chem C 122(5):2696–2703. https://doi.org/10.1021/acs.jpcc.7b10237
Magano J, Dunetz JR (2011) Large-scale applications of transition metal-catalyzed couplings for the synthesis of pharmaceuticals. Chem Rev 111(3):2177–2250. https://doi.org/10.1021/cr100346g
Martin R, Buchwald SL (2008) Palladium-catalyzed Suzuki−Miyaura cross-coupling reactions employing dialkylbiaryl phosphine ligands. Acc Chem Res 41(11):1461–1473. https://doi.org/10.1021/ar800036s
Mehdi A, Reyé C, Brandès S, Guilard R, Corriu RJP (2005) Synthesis of large-pore ordered mesoporous silicas containing aminopropyl groups. New J Chem 29(7):965–968. https://doi.org/10.1039/B502848P
Mello MR, Phanon D, Silveira GQ, Llewellyn PL, Ronconi CM (2011) Amine-modified MCM-41 mesoporous silica for carbon dioxide capture. Microporous Mesoporous Mater 143(1):174–179. https://doi.org/10.1016/j.micromeso.2011.02.022
Molnár A, Papp A (2017) Catalyst recycling—a survey of recent progress and current status. Coord Chem Rev 349:1–65. https://doi.org/10.1016/j.ccr.2017.08.011
Nale DB, Rath D, Parida KM, Gajengi A, Bhanage BM (2016) Amine modified mesoporous Al2O3@MCM-41: an efficient{,} synergetic and recyclable catalyst for the formylation of amines using carbon dioxide and DMAB under mild reaction conditions. Catal Sci Technol 6(13):4872–4881. https://doi.org/10.1039/C5CY02277K
Ncube P, Hlabathe T, Meijboom R (2015) Palladium nanoparticles supported on mesoporous silica as efficient and recyclable heterogenous nanocatalysts for the Suzuki C-C coupling reaction. J Clust Sci 26(5):1873–1888. https://doi.org/10.1007/s10876-015-0885-7
Nicolaou KC, Bulger PG, Sarlah D (2005) Palladium-catalyzed cross-coupling reactions in total synthesis. Angew Chemie Int Ed 44(29):4442–4489. https://doi.org/10.1002/anie.200500368
Nilsson J, Carlsson P-A, Fouladvand S, Martin NM, Gustafson J, Newton MA, Lundgren E, Grönbeck H, Skoglundh M (2015) Chemistry of supported palladium nanoparticles during methane oxidation. ACS Catal 5(4):2481–2489. https://doi.org/10.1021/cs502036d
Noël T, Buchwald SL (2011) Cross-coupling in flow. Chem Soc Rev 40(10):5010–5029. https://doi.org/10.1039/C1CS15075H
Parida KM, Rath D (2009) Amine functionalized MCM-41: An active and reusable catalyst for Knoevenagel condensation reaction. J Mol Catal A Chem 310(1):93–100. https://doi.org/10.1016/j.molcata.2009.06.001
Pujari SP, Scheres L, Marcelis ATM, Zuilhof H (2014) Covalent surface modification of oxide surfaces. Angew Chemie Int Ed 53(25):6322–6356. https://doi.org/10.1002/anie.201306709
Rao N, Wang M, Shang Z, Hou Y, Fan G, Li J (2018) CO2 adsorption by amine-functionalized MCM-41: a comparison between impregnation and grafting modification methods. Energy Fuels 32(1):670–677. https://doi.org/10.1021/acs.energyfuels.7b02906
Rieger B, Baugh LS, Kacker S, Eds SS (2003) Titanium and zirconium in organic synthesis applied homogeneous catalysis with organometallic compounds transition metals for organic synthesis
Sakamoto J, Rehahn M, Wegner G, Schlüter AD (2009) Suzuki polycondensation: polyarylenes à la carte. Macromol Rapid Commun 30(9–10):653–687. https://doi.org/10.1002/marc.200900063
Saptal VB, Saptal MV, Mane RS, Sasaki T, Bhanage BM (2019) Amine-functionalized graphene oxide-stabilized Pd Nanoparticles(Pd@APGO): a novel and efficient catalyst for the Suzuki and carbonylative Suzuki−Miyaura coupling reactions. ACS Omega 4:643–649. https://doi.org/10.1021/acsomega.8b03023
Sawai K, Tatumi R, Nakahodo T, Fujihara H (2008) Asymmetric Suzuki-Miyaura coupling reactions catalyzed by chiral palladium nanoparticles at room temperature. Angew Chemie 120(36):7023–7025. https://doi.org/10.1002/ange.200802174
Sheldon RA, Wallau M, Arends IWCE, Schuchardt U (1998) Heterogeneous catalysts for liquid-phase oxidations: philosophers’ stones or Trojan horses? Acc Chem Res 31(8):485–493. https://doi.org/10.1021/ar9700163
Singha S, Sahoo M, Parida KM (2011) Highly active Pd nanoparticles dispersed on amine functionalized layered double hydroxide for Suzuki coupling reaction. Dalton Trans 40:7130–7132. https://doi.org/10.1039/C1DT10697J
Skotheim TA, Reynolds J (2006) Conjugated polymers: theory, synthesis, properties, and characterization, 3rd edn. CRC Press
Surry DS, Buchwald SL (2011) Dialkylbiaryl phosphines in Pd-catalyzed amination: a user{’}s guide. Chem Sci 2(1):27–50. https://doi.org/10.1039/C0SC00331J
Trzeciak AM, Augustyniak AW (2019) The role of palladium nanoparticles in catalytic C-C cross-coupling reactions. Coord Chem Rev 384:1–20. https://doi.org/10.1016/j.ccr.2019.01.008
Vinu A, Hossain KZ, Ariga K (2005) Recent advances in functionalization of mesoporous silica. J Nanosci Nanotechnol 5(3):347–371. https://doi.org/10.1166/jnn.2005.089
Weng Z, Yu T, Zaera F (2018) Synthesis of solid catalysts with spatially resolved acidic and basic molecular functionalities. ACS Catal 8(4):2870–2879. https://doi.org/10.1021/acscatal.7b04413
Xu M, Wei M (2018) Layered double hydroxide-based catalysts: recent advances in preparation, structure, and applications. Adv Funct Mater 28(47):1802943. https://doi.org/10.1002/adfm.201802943
Zhao J, Ye J, Zhang YJ (2013) Stereospecific allyl-aryl coupling catalyzed by in situ generated palladium nanoparticles in water under ambient conditions. Adv Synth Catal 355(2–3):491–498. https://doi.org/10.1002/adsc.201200704
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One of the authors Seema Patil, is grateful to the Department of Science and Technology (DST), New Delhi, Government of India, for the award of the Women Scientist Scheme-A (WOSA), File no. SR/WOS-A/CS-85/2018.
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Patil, S.P., Jadhav, S.N., Inamdar, F.A. et al. Recyclable Pd nanoparticles immobilized on amine functionalized LDH for the Suzuki–Miyaura cross-coupling reaction. Chem. Pap. 77, 5555–5569 (2023). https://doi.org/10.1007/s11696-023-02885-2
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DOI: https://doi.org/10.1007/s11696-023-02885-2