Magnetically separable and recyclable Fe3O4@SiO2/isoniazide/Pd nanocatalyst for highly efficient synthesis of biaryls by Suzuki coupling reactions

doi:10.1016/j.jcis.2017.04.054

Journal of Colloid and Interface Science

Volume 501, 1 September 2017, Pages 175-184

https://doi.org/10.1016/j.jcis.2017.04.054 Get rights and content

Abstract

This report contains the procedure implemented in the preparation of Fe₃O₄@SiO₂/isoniazide/Pd as a novel magnetic nanocatalyst, in which isoniazide groups are utilized (as linkers) to secure palladium nanoparticles (Pd NPs) to the Fe₃O₄ exterior without agglomeration. The resultant catalyst was characterized through performing transmission electron microscopy (TEM), scanning electron microscopy (SEM), wavelength-dispersive X-ray spectroscopy (WDX), X-ray powder diffraction (XRD), Fourier transform infrared (FTIR), inductively coupled plasma (ICP), Energy-dispersive X-ray spectroscopy (EDS), vibrating sample magnetometer (VSM) and X-ray photoelectron spectroscopy (XPS). The catalytic behavior of Fe₃O₄@SiO₂/isoniazide/Pd was investigated to synthesis of biaryl compounds by Suzuki coupling reactions. Interestingly, the novel catalyst was able to be recovered and recycled six times without any noticeable loss in activity.

Graphical abstract

Introduction

Palladium has the greatest versatility of all catalysts used in the construction of carbon single bond carbon bonds in Heck, Suzuki, Sonogashira or Still coupling reactions, and is hence the most widely applied catalyst in these reactions [1]. As a homogeneous catalyst, Pd with phosphine ligands, carbene ligands and other coordinates often exhibited higher TON (turnover number) and enhanced catalytic activity for inactive chloride substances, particularly in Suzuki coupling reactions [2]. Despite this, for large scale applications, homogeneous catalytic systems result in greater difficulties including the purification of the final products and recycling of the expensive catalysts. Fortunately, the heterogeneous catalytic systems provide alternative strategies that overcome the above difficulties [3].

Conventional heterogeneous catalysts utilized palladium nanoparticles immobilized on polymeric organic [4], [5] or inorganic [6], [7] supports. Their catalytic behavior strongly depended on the size of Pd particles. Particular heterogeneous Pd catalyst demonstrated lower catalytic activity due to aggregation and leaching of Pd species or particles. Therefore, to assist in dispersion and stabilizing the supported palladium nanoparticles, nature of catalyst supports, advanced preparation procedures and essential functionalization should be considered appropriately [8], [9].

Palladium nanoparticles immobilized on inorganic materials such as silica [10], [11], carbon [12], and metal oxides [13] would be one promising solution. Due to the convenient and simple recovery of the catalyst compete by mean of an external magnetic field, their interesting structure, large surface area, eco-friendly, relatively non-toxic compound, high coercively, low Curie temperature, Fe₃O₄ NPs has become a desirable solid support for Pd nanoparticles [13], [14], [15], [16], [17], [18], [19], [20], [21], [22].

There have been a multitude of reports containing descriptions of the use of magnetic nanocomposites for the immobilization of Pd nanoparticles, the catalytic activity of Pd nanoparticles can be retained, and the stability also can be improved to some extent [23], [24], [25]. In an attempt to continue extending the efficient and environmentally benign heterogeneous catalysts [26], we shall report a basic preparation of palladium nanoparticles incorporated into Fe₃O₄@SiO₂/isoniazide/Pd nanocomposite as a novel magnetically recoverable heterogeneous catalyst (Scheme 1). The C single bond C coupling reaction was catalyzed using this recyclable heterogeneous catalyst in an aqueous solvent through Suzuki reactions (Scheme 2). Most significantly, the synthesized Fe₃O₄@SiO₂/isoniazide/Pd nanocomposite demonstrated an excellent magnetic property, and was thus easily separable from the reaction mixture by use of a magnet. Through utilizing this property it was reused for six cycles without any loss in catalytic activity, highlighting its potential application in industry.

Section snippets

Materials and apparatus

Isoniazide, Ferric chloride hexahydrate (FeCl₃·6H₂O), ferrous chloride tetrahydrate (FeCl₂·4H₂O), PdCl₂, tetraethyl orthosilicate (TEOS), chloropropyl teriethoxysilane (CPTES), NaBH₄, phenyl boronic acid and arylhalides were obtained from Aldrich. Other reagents and compounds were purchased from Merk. The crystalline structures of the samples were evaluated by X-ray diffraction (XRD) analysis on a Bruker D8 Advance diffractometer with CuKα radiation at 40 kV and 20 mA. Fourier transform infrared

Characterization of Fe₃O₄@SiO₂/isoniazide/Pd

The reactions undergone for the synthesis of the catalyst Fe₃O₄@SiO₂/isoniazide/Pd is shown in Scheme 1. The content of linked isoniazide on Fe3O4@SiO2 was determined by elemental analysis which revealed a loading of ∼0.18 mmol of isoniazide per gram of Fe₃O₄. Additionally, the Pd content of the catalyst as estimated by AAS was 0.21 ± 0.001 mmol g⁻¹. This indicated that all of the anchored organic ligand moieties have efficiently coordinated with Pd ions, providing catalytically active sites. The

Conclusion

In Summary, we have established an effective practice for the synthesis of Fe₃O₄@SiO₂/isoniazide/Pd nanoparticles. The catalyst was classified through FTIR, XRD, FESEM, TEM, VSM, WDX, EDS and ICP examination. The heterogeneous catalyst displays good catalytic performance in the Suzuki coupling reaction. The beneficial features of the suggested procedure include its generality, high efficiency and ease, which result in short reaction times, high yields, a cleaner reaction profile and

Acknowledgments

We are thankful to Payame Noor University and Pharmaceutical Sciences Branch, Islamic Azad University, Tehran for partial support of this work.

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Regular ArticleMagnetically separable and recyclable Fe3O4@SiO2/isoniazide/Pd nanocatalyst for highly efficient synthesis of biaryls by Suzuki coupling reactions

Abstract

Graphical abstract

Introduction

Section snippets

Materials and apparatus

Characterization of Fe3O4@SiO2/isoniazide/Pd

Conclusion

Acknowledgments

Tetrahedron Lett.

Chem. Rev.

J. Org. Chem.

Am. Chem. Soc.

Organometallics

Organometallics

Tetrahedron Lett.

Chem. Rev.

Appl. Catal. B: Environ.

Fuel Process. Technol.

Appl. Organomet. Chem.

Tetrahedron Lett.

Catal. Commun.

J. Colloid Inter. Sci.

Energies

Catal. Today

Catal. Commun.

RSC Adv.

Rsc. Adv.

ACS Appl. Mater. Inter.

ChemCatChem

Powder Technol.

Hydrometallurgy

J. Organomet. Chem.

Eur. J. Org. Chem.

Appl. Organomet. Chem.

J. Braz. Chem. Soc.

Regular Article
Magnetically separable and recyclable Fe₃O₄@SiO₂/isoniazide/Pd nanocatalyst for highly efficient synthesis of biaryls by Suzuki coupling reactions

Characterization of Fe₃O₄@SiO₂/isoniazide/Pd