Pd^II on Guanidine-Functionalized Fe₃O₄ Nanoparticles as an Efficient Heterogeneous Catalyst for Suzuki–Miyaura Cross-Coupling and Reduction of Nitroarenes in Aqueous Media

Abstract

This paper presents guanidine-functionalized Fe 3 O 4 magnetic nanoparticle-supported palladium (II) (Fe 3 O 4 @Guanidine-Pd) as an effective catalyst for Suzuki–Miyaura cross-coupling of aryl halides using phenylboronic acids and also for selective reduction of nitroarenes to their corresponding amines. Fe 3 O 4 @Guanidine-Pd synthesized is well characterized using FT-IR spectroscopy, XRD, SEM, TEM, EDX, thermal gravimetric analysis, XPS, inductively coupled plasma-optical emission spectroscopy, and vibrating sample magnetometry analysis. The prepared Fe 3 O 4 @Guanidine-Pd showed effective catalytic performance in the Suzuki–Miyaura coupling reactions by converting aryl halides to their corresponding biaryl derivatives in an aqueous environment in a shorter reaction time and with a meagerly small amount of catalyst (0.22 mol %). Also, the prepared Fe 3 O 4 @Guanidine-Pd effectively reduced nitroarenes to their corresponding amino derivatives in aqueous media at room temperature with a high turnover number and turnover frequency with the least amount of catalyst (0.13 mol %). The most prominent feature of Fe 3 O 4 @Guanidine-Pd as a catalyst is the ease of separation of the catalyst from the reaction mixture after the reaction with the help of an external magnet with good recovery yield and also reuse of the recovered catalyst for a few cycles without significant loss in its catalytic activity.

The Transfer Hydrogenation of Cinnamaldehyde Using Homogeneous Cobalt(II) and Nickel(II) (E)-1-(Pyridin-2-yl)-N-(3-(triethoxysilyl)propyl)methanimine and the Complexes Anchored on Fe3O4 Support as Pre-Catalysts: An Experimental and In Silico Approach

“…From the TEM micrographs, the nano-catalysts are agglomerated into spherical shapes. This tendency is not surprising, given the nanoparticles’ small size and magnetic properties [ 24 ]. The appearance of dark shades in the images (b–e) implies that the electron beam did not penetrate the sample, which could be a result of the homogeneous phase of the catalyst that is attached to the support occluding the electron beam.…”

“…Figure 5 a shows the overview spectra of the composition of the catalyst Fe 2 O 3 @C2 with atomic percentage, whereas the analysis for the elements Fe, Cl, Si are shown in Figure 5 c–e. We can fit the N 1s spectrum, Figure 5 b, into a typical peak corresponding to a metal-N species (399.1 eV); these species in Ni-N-C support the dispersion of Ni in the form of Ni-N coordination [ 1 , 24 ].…”

Chitosan‐Ethylenediaminetetraacetic acid‐palladium composite for the Suzuki–Miyaura reaction

“…SEM images of the catalyst after the second run revealed the agglomeration of Pd nanoparticles on the surface of the catalyst, which is the major reason for the drop in the product yields as shown in Figure 8. The yield after the second run reaction was still high (>90%) and dropped to 80% after the fifth run but dramatically decreased to 50% after the sixth 1 a CS-NNSB-Pd(II) (0.006) -50 c 0.08 97 Baran [28] 2 ImmPd-MNPs (0.14) TBAB/H 2 O r.t. 0.3 93 Hajipour and Tavangar-Rizi [29] 3 CS-Biguanidine/Pd (0.15) EtOH/H 2 O 40 1 98 Veisi et al [32] 4 Pd@Cell-EDTA (0.05) EtOH/H 2 O 78 0.5 96 Xu et al [11] 5 PdNPs@chitosan (0.1) TBAB 90 5 97 Cotugno et al [17] 6 PdNPs/GO-TETA (0.01) DMF/H 2 O 90 0.4 98 Mirza-Aghayan et al [19] 7 F e 3 O 4 @SiO 2 /PropylSB@Pd (0.1) H 2 O/EtOH 80 c 0.5 92 Hasan et al [6] 8 F e 3 O 4 /CS-Me@Pd (0.003) EtOH/H 2 O 50 30 98 Wang et al [36] 9 Cell-Sc-Pd(II) (0.002) EtOH/H 2 O 70 1.5 74 Pharande et al [12] 10 Fe 3 O 4 -CS@tet-Pd(II) EtOH/H 2 O 90 2.2 91 Nasrollahzadeh et al [40] 11 a Fe 3 O 4 @Guanidine-Pd (0.22) H 2 O 70 0.5 90 Halligudra et al [8] 12 Fe 3 O 4 @SiO 2 -TCT-GA-Pd(0) (0.12) EtOH/H 2 O 50 1.5 95 Eslahi et al [9] 13 PdNPs@CS/δ-FeOOH (0.05) EtOH/H 2 O r.t. 3 91 Çalıs ¸kan and Baran [21] 14 Fe 3 O 4 @MCM41@NHC@Pd (0.01) run. From these results, it can be concluded that the catalyst was effective for five runs.…”

“…[1][2][3] Among the crosscoupling reactions, the Suzuki-Miyaura reaction is one of the powerful tools to create a carbon-carbon bond from the cross-coupling of aryl boronic acid and aryl halides using a palladium catalyst to synthesize biaryls for industrial uses related to pharmaceuticals, agrochemicals, polymers, and materials. [4,5] Recently, many research groups have demonstrated the use of various kinds of materials as catalyst support for the Suzuki-Miyaura reaction, including organic and inorganic compounds such as metal oxides, [6][7][8][9][10] polymers, [11][12][13][14][15][16][17][18] carbon materials, [19,20] and composite materials. [21,22] Among these support materials, natural polymers have attracted much attention due to their availability, nontoxicity, biodegradability, and low cost.…”

“…Recently, many research groups have demonstrated the use of various kinds of materials as catalyst support for the Suzuki–Miyaura reaction, including organic and inorganic compounds such as metal oxides, [ 6–10 ] polymers, [ 11–18 ] carbon materials, [ 19,20 ] and composite materials. [ 21,22 ] Among these support materials, natural polymers have attracted much attention due to their availability, nontoxicity, biodegradability, and low cost.…”