Palladium supported terpyridine modified magnetic nanoparticles as an efficient catalyst for carbon-carbon bond formation

https://doi.org/10.1016/j.jorganchem.2021.121682Get rights and content

Highlights

  • Palladium Supported Terpyridine Modified Magnetic Nanoparticles as an effective and novel nano organometalic compounds were synthesized.

  • Pd@terPy@SPION nanoparticles as an Efficient Catalyst for Carbon-Carbon Bond Formation.

  • This procedure has advantages such as reduced reaction time and higher yield.

  • Pd@terPy@SPION is non-toxic, easy handling and reusable, simple work-up procedure, short reaction time, high yields of product with better purity and green aspect by avoiding toxic catalyst and hazardous solvent.

  • Easy of recovery and reuse of catalyst make this procedure economic.

Abstract

In this paper, a novel catalyst is designed, synthesized and characterized based on the functionalization of magnetic iron oxide nanoparticles by terpyridine as a ligand for the immobilization of palladium. The catalyst is fully characterized by several characterization methods, including SEM, FTIR, DLS, VSM, EDS and XRD analysis. The results of the characterization techniques proved the successful synthesis of the desired catalyst. The applicability of the catalyst was evaluated in Heck and Suzuki reaction. The catalyst showed very good activity through the mentioned carbon-carbon bond formation reactions. The catalyst is magnetically recoverable and could be separated simply from the reaction media by an external magnet. The use of the catalyst in 10 sequential reactions did not show any significant loss in the activity of the catalyst.

Introduction

Carbon-carbon bond formation is a key reaction in organic chemistry. Several efforts have focused on extending methods for these reaction with higher efficiency in milder reaction conditions. Palladium catalyzed cross coupling reaction of aryl halides with alkenes (known as Mizoroki-Heck reaction), or with phenyl boronic acids (known as Suzuki reaction) are of high interest among carbon-carbon bond formation reactions [1], [2], [3], [4]. Palladium is the most popular catalyst for the mentioned reactions using various ligands, such as bis pyrimidines [5,6], thiourea [7], β-diimines [8] and etc. For increasing the activity and reusability of palladium catalyst in Mizoroki-Heck and Suzuki reaction, an approach is to immobilize this metallic catalyst onto the modified solid supports [9], [10], [11], [12], [13], [14]. Among several materials, which have been used as support for the immobilization of palladium, magnetic iron oxide nanoparticles are common candidates, due to their unique properties, including chemical and thermal stability, ease of separation from the reaction mixture and recovery, ease of functionalization and facility of the synthesis and fabrication [15], [16], [17], [18], [19]. Apart from applications in catalysis, superparamagnetic nanoparticles are of magnetic materials, which have wide applications in several areas, including semiconductors [20,21], medical imaging and therapy [22,23], drug delivery [24,25] and the synthesis of polymer composites with improved properties [26], [27], [28].

Regarding the significance of Mizoroki-Heck and Suzuki reaction in carbon-carbon bond formation reactions and the versatility of superparamagnetic iron oxide nanoparticles in catalysis, in this paper modified iron oxide nanoparticles are used as a support for immobilization of palladium catalyst. Superparamagnetic iron oxide nanoparticles are modified by terpyridine as a ligand for the immobilization of palladium catalyst (denoted Pd@terPy@SPION). The catalyst is applied in Mizoroki-Heck and Suzuki carbon-carbon bond formation reactions.

Section snippets

Results and discussion

In continuation of our work concerning the synthesis of heterocyclic and pharmaceutical compounds under mild and green protocols [29], [30], [31], [32], [33], [34], [35], [36], [37] we herein report a green procedures for Mizoroki-Heck and Suzuki reaction using of Pd@terPy@SPION nanoparticle as a novel nano-catalyst. In this paper, Pd@terPy@SPION is designed and synthesized by the immobilization of palladium onto terpyridine functionalized Superparamagnetic iron oxide nanoparticles. For the

General remarks

All the chemicals, reagents and solvents were purchased from Merck, Across, and Scharlau. SEM image of the catalyst was recorded by a VEGATESCAN-LMU instrument. The particle size of the samples was analyzed by Nanotrac Wave from Microtrac DLS instrument. FT-IR spectra were recorded on a Bruker Tensor 27 FTIR spectrophotometer. Nuclear magnetic resonance spectra were recorded on a Bruker FT- 250 spectrometers using tetramethyl silane (TMS) as internal standard in pure deuterated solvents.

General procedure for the Heck/Sonogashira reactions

A mixture containing aryl halide (1.0 mmol), alkene (1.1 mmol)/ phenylboronic acid (1.0 mmol), sodium acetate (1.5 mmol) and Pd@terPy@SPION (5 mg, 0.11 mol%) was stirred in H2O (3.0 mL) at room temperature. The reaction performance was monitored by TLC. After the reaction was completed, a magnet was applied for isolation of the catalyst. The solution collected and the product was extracted with ethyl acetate. The organic phase was dried over Na2SO4. The solvent was evaporated and the product

Conclusion

In this paper, a novel catalyst is designed and synthesized based on the immobilization of palladium on magnetic iron oxide nanoparticles. For this purpose, superparamagnetic iron oxide nanoparticles were prepared by the co-precipitation of Fe2+ and Fe3+ in basic medial the synthesized SPION were then encapsulated by SiO2. The nanoparticles were functionalized by terpyridine moieties, which were used a ligand for palladium. The catalyst is characterized by several methods, including SEM, DLS,

Declaration of Competing Interest

We declare that none of the authors of this manuscript are official representatives or on behalf of the government. So, we confirm that the research presented in the submitted paper is not funded by, or on behalf of, the State or Government of Iran.

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

The authors are not any Conflict of Interest.

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