Recyclable LaF₃·Pd nanocatalyst in Suzuki coupling: green synthesis of biaryls from haloarenes and phenylboronic acids

Abstract

Herein we prepared the novel LaF₃·Pd nanocatalyst characterized by XRD and TEM analysis. The nanocatalyst was applied in Suzuki coupling reaction for the synthesis of biaryls in aqueous medium from readily available aryl halides (bromides and iodides) and substituted phenylboronic acids in the presence of K₂CO₃ as the base at 70 °C. The present method is capable of giving the C–C coupled product in good to excellent yields (up to 97%). The reactions were conducted under green conditions in aqueous medium and the nanocatalyst used in this study was recyclable. The recyclability and reusability of the catalyst was checked for seven consecutive cycles without significant loss in reactivity.

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Introduction

C(sp²)–C(sp²) bond forming reactions¹ are very important strategies to construct complex scaffolds in natural products,² drug discovery, medicinal chemistry,^2b functional materials, etc. Various transition metals have been used extensively in many reactions i.e., C–H activations,³ cross-coupling reactions, etc. to construct C–C bonds having moderate to complex motifs in many usual organic transformations. Palladium-catalyzed coupling reactions play a very important role in organic synthesis. The 2010 Nobel prize in chemistry supports the popularity, success, and importance of this field.⁴ Among all, the Suzuki coupling reaction is one of the most celebrated and frequently encountered reactions in the laboratory as well as industry for the construction of C–C bonds to synthesize biaryls.⁵ Biaryl-containing scaffolds as a backbone constitute a subunit in many organic frameworks, and are widely distributed in many natural products,⁶ functional materials, catalysts-ligands,⁷ pharmaceuticals and drugs,⁸ agrochemicals,⁹ etc. (Fig. 1). The biaryl-based scaffolds have been documented to exhibit a broad range of biological activities.¹⁰

Fig. 1 Representative examples of biaryls in naturally occurring molecules, catalysts, drugs, and agrochemicals with biaryl scaffolds.

Discovering greener approaches in organic synthesis is always a challenge to organic chemists. The demand for developing green and sustainable methods has been increasing in recent years. In this context, the use of green energy, solvents, one-pot processes with minimal waste production with high atom and step-economy, and the use of recyclable nanocatalysts are considered to be the better alternatives.^5e In the literature the Suzuki coupling is well documented with the combination of various homogeneous catalysts and ligands, which also comes with some limitations such as expensive ligands, additional steps for ligand synthesis, metal contamination in the products, metal leaching.^5d In recent years, transition metal-derived nanocatalysts have received a great deal of attention from synthetic chemists because of their high activity, and sustainable aspects as compared to homogeneous catalysts. They are frequently used in organic synthesis.¹¹ In this backdrop, the Pd-based nanoparticles proved to be an excellent candidate in the coupling reaction for the formation of C–C bonds. Several coupling reactions such as Suzuki–Miyaura, Heck and Sonogashira reactions have been successfully conducted in the presence of Pd-nanocatalysts.¹²

The lanthanide-based nanoparticles (LNPs)^13–15 are widely known for their optical properties and they find applications in bioimaging, optical sensing, image-guided therapy, biosensing, and optogenetics. Apart from biological applications, the LNPs have been utilized as efficient catalysts in organic synthesis.^16–18 Therefore, in continuation of our research interest in lanthanide-based nanoparticles and C–C bond forming methodology development,¹⁹ we are interested in utilizing the LNP (LaF₃·Pd)₃ as a catalyst to carry out Suzuki coupling reactions and to our delight the LNP showed good catalytic activity and it was recovered from the reaction system and reused up to seven consecutive runs without significant loss of reactivity.

Results and discussion

Synthesis and characterization of LaF₃·Pd nanocatalyst

The La–Pd bimetallic nanoparticles were prepared from the reaction of La₂O₃, Pd(OAC)₂, and NH₄F in the presence of 50% NH₄OH at 120 °C in autoclave as displayed in Scheme 1.

Scheme 1 Preparation of the LaF₃·Pd 5 at % nanoparticles.

XRD study

XRD patterns of synthesized LaF₃·Pd is shown in Fig. 2. From the diffraction pattern it is obvious that the nanoparticles are highly crystalline and the diffraction peaks correspond to that of pure LaF₃ hexagonal system (JCPDS No. 076-0510). The lattice parameters, cell volume and particle size calculated using Scherrer equation are given in the Table 1. The peaks from other phases were not detected in the as-prepared sample indicating that the as-prepared sample is pure. However the nanoparticles after used as catalyst some new peaks are appeared (marked with asterisk) indicating changes in the LaF₃ nanoparticles. This change may be due to the formation of some LaF₃ to LaFCO₃ nanoparticle (JCPDS-074-0985) since K₂CO₃ is used in the reaction.

Fig. 2 XRD pattern of LaF₃·Pd.

Table 1 The lattice parameters, cell volume and particle size of LaF₃·Pd

	a (Å)	b (Å)	c (Å)	Cell volume	Particle size
JCPDF-076-0510	4.148	4.148	7.354	109.58
LaF3	4.157	4.157	7.352	110.06	17.05
LaF3:Pd	4.150	4.150	7.360	109.78	11.50
LaF3:Pd (after used)	4.161	4.161	7.350	110.21	14.17

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TEM image

The TEM image (Fig. 3b) of LaF₃·Pd nanoparticles reveal that particles are spherical in shape with a diameter maximum about 8 nm (Fig. 3d). The high magnification TEM image (Fig. 3a) shows the lattice fringes of the nanoparticles corresponding to the lattice fringes (100) and (101) plane of hexagonal Lanthanum fluoride (JCPDS No. 076-0510). The lattice planes are also assigned in the SAED pattern Fig. 3c corresponding to the (100), (101), (110) and (112) plane. The lattice fringes in the HRTEM and SAED pattern indicated the well crystallinity of the particles.

Fig. 3 (a) HRTEM image (b) TEM image (c) SAED pattern (d) histogram of particle size of LaF₃·Pd.

Palladium doped LaF₃ nanoparticles for catalysis

From the X-ray photoelectron spectroscopy (XPS) spectrum in the Fig. 4a and b it clearly indicates the presence of La and Pd ions in the prepared nanoparticles. The La 3d binding energy around 853 and 837 eV of La 3d_3/2 and La 3d_5/2 respectively. From the Pd 3d scan the existence of metallic Pd(0) and Pd(II) is also confirmed where the binding energies of 3d_5/2 are 336 eV, 337 eV and for that of 3d_3/2 are 342 eV, 343 eV respectively. The PP at% are found to be La 3d_5/2 = 0.37 at%, F 1s = 1.8 at%, Pd 3d_3/2 = 0.09 and Pd 3d_5/2 = 0.06 at% (Fig. 4).

Fig. 4 (a) X-ray photoelectron spectroscopy spectra (b) magnified XPS of LaF₃·Pd.

Optimization of reaction condition using the LaF₃·Pd nanocatalyst

With the LNP (LaF₃·Pd) in hand, we were interested in exploring the catalytic efficiency of the LNP in Suzuki coupling. With this objective, we commenced the optimization study for the Suzuki coupling reaction by taking 4-bromophenol 1f (1.0 mmol), and phenylboronic acid 2a (1.5 mmol) as the standard substrates in the presence of 40 mg of the catalyst, in the presence of NaOH in aqueous medium under room temperature, pleasingly 3f was isolated in 81% yield (entry 1, Table 2). The structure of 3f was characterized by recording ¹H and ¹³C NMR spectra. Then by keeping all the parameters same and varying the base such as KOH, K₂CO₃, Na₂CO₃, and Et₃N the product 3f was isolated in 83%, 97%, 82%, and 84% yields respectively (entries 2–5, Table 2). From the screening of the bases the K₂CO₃ was found as the best choice. Next, to check the optimum amount of catalyst by keeping all the parameters the same and varying the catalyst loading, the amount of catalyst was decreased gradually from 30 mg to 15 mg and found that 15 mg is the optimum amount of catalyst needed for the current study (entries 6–8, Table 2). Then we turned our attention to check whether any other solvent can be employed to get enhanced yield and with less reaction time. So various solvents such as dioxane, DMSO, and DMF were screened by keeping the catalyst loading 15 mg and all other parameters constant (entries 9–11, Table 2), and found that no solvent gives better results than H₂O. With this optimum condition for 3f (15 mg catalyst, H₂O, K₂CO₃, RT for 1 hour), we turned our attention to study the substrate scope. Surprisingly, the optimum condition is not suitable for 3a (entry 1, Table 3).

Table 2 Optimization Table with 1f

Entry	Catalyst loading (mg)	Base (equiv.)	Solvent	Temperature (°C)	Time (hours)	Yield^a^,^b (%)
a Reaction conditions: 1f (1 mmol), 2a (1.5 mmol) in 3 mL of solvent.b Isolated yield.
1	40	NaOH (2)	H2O	RT	1	81
2	40	KOH (2)	H2O	RT	1	83
3	40	K2CO3 (2)	H2O	RT	1	97
4	40	Na2CO3 (2)	H2O	RT	1	82
5	40	Et3N (2)	H2O	RT	1	84
6	30	K2CO3 (2)	H2O	RT	1	97
7	20	K2CO3 (2)	H2O	RT	1	97
8	15	K2CO3 (2)	H2O	RT	1	97
9	15	K2CO3 (2)	Dioxane	RT	1	90
10	15	K2CO3 (2)	DMSO	RT	1	81
11	15	K2CO3 (2)	DMF	RT	1	79

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Therefore, optimum conditions were further investigated by taking bromobenzene 1a, and 2a. Under the study, the base, catalyst loading, and the solvent were kept constant, and increased the temperature from 50–100 °C (entries 1–5, Table 3). At 50 °C, the product 3a was isolated in 62% yield (entry 2, Table 3). Then with increase in temperature to 70 °C 3a was isolated in 85% yield (entry 3, Table 3) and further increase in temperature up to 100 °C improved the product yield further (entries 4 and 5, Table 3). Thus, 70 °C was found to be optimum temperature for the reaction (entry 3, Table 3). To our delight, this optimum condition worked well for all the substrates under the study.

Table 3 Optimization table with 1a

Entry	Catalyst loading (mg)	Base (equiv.)	Solvent	Temperature (°C)	Time (hours)	Yield^a^,^b (%)
a Reaction conditions: 1a (1 mmol), 2a (1.5 mmol) in 3 mL of solvent.b Isolated yield.
1	15	K2CO3 (2)	H2O	RT	40	8
2	15	K2CO3 (2)	H2O	50	4	62
3	15	K2CO3 (2)	H2O	70	4	85
4	15	K2CO3 (2)	H2O	80	4	85
5	15	K2CO3 (2)	H2O	100	4	85

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Then, to check the electronic and steric effect, at first the bromobenzenes with electron donating substituents 1-bromo-4-methylbenzene 1b was reacted with 2a at 70 °C and 80% yield of the product was observed. Next, bromobenzene with 4-OMe and 3-OMe substituent were reacted with phenylboronic acid 2a and pleasingly the corresponding products 3c and 3d were isolated in 77% and 85% yields. Next, the 2-OH and 4-OH substituted bromobenzene were reacted with 2a. The respective biaryls 3e and 3f were isolated in 79% and 97% yields. Then the haloarenes with various electron withdrawing groups were tested. 4-CN substituted bromobenzene gave 75% yield of the corresponding biaryl 3g. Iodobenzene with 4-NO₂ substitution resulted the corresponding biaryl 3h in 95% yield. Other electron withdrawing groups on the bromobenzene such as 2-CHO, 4-CHO, 3-CHO, 4-C(O)Me. 3-C(O)Me were also capable of resulting the corresponding biphenyls 3i, 3j, 3k, 3l, 3m in 82%, 93%, 75%, 85%, 88% yields respectively. Next, the fused biphenyls were also screened for synthesizing the biaryl systems. For this, 7-bromonaphthalen-2-ol and 1-bromonaphthalene were subjected to react with 2a. Pleasingle the corresponding fused aromatics based biaryls 3n and 3o were isolated in good yields (78% and 68% respectively). The heteroaromatic systems are important candidates in drug discovery, thus to check whether the present method can be applied for coupling with heteroaromatic halides, a reaction was performed between 2-bromo-4-methylpyridine and 2a. The corresponding coupled product 3p was isolated in 66% yield. After checking the substrate scope of haloarenes, we then turned our attention to check the substrate scope for the substituted phenylboronic acid. For that We have reacted 4-nitroiodobenzene with the phenylboronic acid with 4-Me and 4-OMe substitution and the expected coupled products 3q and 3r were obtained in 65% and 70% yield. Then, bromobenzene was reacted with the phenylboronic acid with 4-Me, 4-CF₃ and 4-OMe substitutions and the respective coupled products 3s, 3t and 3u were isolated in 75%, 75% and 78% yields respectively. Next, 4-bromo-1,1′-biphenyl was reacted with 2a and pleasingly the coupled product 1,1′:4′,1′′-terphenyl 3v was isolated in 67% yield. Apart from the bromo and iodobenzene derivatives, we have also studied the scope of chloro aromatic and heteroaromatics. The 2-amino-5-chloropyridine and 4-chloroaniline were subjected to react with phenylboronic acid 2a in the developed reaction condition. But the coupled product 3w and 3x were not formed (Scheme 2).

Scheme 2 Substrate scope for the LaF₃·Pd nanocatalyzed synthesis of biaryls. ^aReaction conditions: 1 (1.0 mmol), 2 (1.5 mmol), LaF₃·Pd (15 mg), K₂CO₃ (2.0 mmol) and H₂O (3.0 mL) were added in a 10 mL round-bottom flask and fitted with reflux condenser. The reaction mixture was stirred vigorously at 70 °C until the completion of the reaction (by TLC monitoring). ^bIn case of 3f the reaction was performed at room temperature. NR: no reaction.

Scale-up experiment

To further check, whether the present method can be applied to synthesize the biaryls in large scale, a reaction was performed by taking the 4-bromophenol 1f (10 mmol), phenylboronic acid 2a (15 mmol) at room temperature. To our delight, the corresponding biaryl 3f was isolated in 95% yield (1.6 g) (Scheme 3).

Scheme 3 Gram scale synthesis of 3f.

Recyclability test

The nanocatalysts in recent years are becoming popular for their recyclability up to several cycles. Also owing to easy to handle, sustainable and green aspect, they are becoming popular in industries. Thus to check whether the present nanocatalyst LaF₃·Pd can be recycled and reused, the reaction was performed by taking 1a (2.0 mmol) and 2a (3.0 mmol) in the presence of 30 mg of the catalyst under the optimized reaction condition. After completion of the reaction, the catalyst was recovered by centrifuge and dried and further utilized in the synthesis of 3a. Pleasingly, the catalyst was recovered and reused for seven consecutive cycles without significant loss in the catalytic activity and the product yield (Table 4).

Table 4 Recyclability of the catalyst and the isolated yields

No. of runs	Catalyst used	Catalyst recovered	Yields (%)
1st run	30 mg	28 mg	84
2nd run	28 mg	27 mg	85
3rd run	27 mg	25 mg	83
4th run	25 mg	24 mg	84
5th run	24 mg	22 mg	83
6th run	22 mg	21 mg	82
7th run	21 mg	19 mg	82

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Comparison

The nanocatalyzed Suzuki reaction is getting attention from synthetic chemists owing to its green aspects such as reusability. In this regard, there are many reports frequently published on the nanocatalyzed C–C bond formation by Suzuki coupling. Thus, to check the efficacy of our catalyst LaF₃·Pd with the recent reported literature, we summarized the results of various nanocatalyzed Suzuki reactions with the present work (Table 5).^20–34 It is clear from the table that the present catalyst is efficient enough for the synthesis of biaryls in terms of product yield and reaction time and also this can be recycled and reused.

Table 5 Comparison of recently reported works with the present work

Sl. no	Catalyst	Reaction condition	Time	Yield	Ref.
1	Nano-Fe3O4@CA-Pd	K2CO3, EtOH : H2O, 75 °C	25 min	Trace-98%	20
2	Fe3O4@SiO2–NHC–Pd(Π) NPs	K2CO3, H2O, 60 °C	1–16 h	69–97%	21
3	5%Pd/TiO2, anatase type	Cs2CO3, DMA, 80 °C, under Ar, sealed, 1000 rpm	24 h	42–98%	22
4	Fe3O4@SiO2-NMIM-Pd	K2CO3, EtOH, 80 °C	1.5–5 h	27–97%	23
5	Ni-TC@ASMNP	K3PO4, dioxane, PPh3, 100 °C	10–15 h	75–97%	24
8	Pd NPs@APC	K2CO3, solvent-free, microwave	5 min	52–99%	25
9	Fe3O4@SiO2–Pd	CaO, EtOH : H2O (1 : 1), 85 °C	20–70 min	87–96%	26
10	Fe3O4@NC/Pd	KOH, H2O, 90 °C	0.5 h	53–99%	27
11	ZrO2@AEPH2-PPh2-Pd(0)	K2CO3, H2O, 80 °C	20 min–24 h	Trace-95%	28
12	Fe3O4@boehmite-NH2-Co^II NPs	KOH, H2O, 80 °C	25 min–9 h	15–95%	29
13	Cu–ninhydrin@GO–Ni MNPs	Na2CO3, H2O, 80 °C	50 min–7 h	89–97%	30
14	Pd/CuFe2O4 nanowires	K2CO3, DMSO, 100 °C	10 min–12 h	27–99%	31
15	Pd-SBT@MCM-41	PEG-400, 80 °C	1–5 h	87–98%	32
16	Pd@CQD@Fe3O4 NPs	t-BuOK, EtOH : H2O (1 : 1) 60–120 °C	2–24 h	88–100%	33
17	Pd@4PVP	K3PO4, EtOH/H2O (3 : 1) 80 °C	3–18 h	29–99%	34
18	LaF3·Pd nanocatalyst	K2CO3, H2O, RT-70 °C	1–4 h	66–97%	This work

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Conclusion

To summarize, we synthesized the LaF₃·Pd 5% nanocatalyst and characterized by XRD and TEM analysis. To check the catalytic efficiency of the synthesized nanocatalyst, we applied the nanocatalyst for the synthesis of biaryls via Suzuki coupling in the aqueous medium, a greener condition. To our delight, the catalyst is efficient enough to result the products in good to excellent yields within 1–4 hours. Also, the catalyst was recycled from the reaction medium and reused for seven consecutive runs without any significant decrease in the catalytic activity and product yield. This green and sustainable aspect of the present method meets the requirement of industrial applications. Thus, we believe the present report will be a valuable addition to the green and sustainable methodologies in synthetic organic transformation.

Data availability

The data that support the finding of the present study are available in ESI‡ of this article.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

B. B. P. is thankful to SERB (SRG/2019/002032), New Delhi, S&T Department Project-Odisha (ST-SCST-0061/2018/2724), UGC (F. 30-484/2019) (BSR) and G. P. is thankful to OURIIP-Odisha for funding. S. S. A. is thankful to CSIR India for junior research fellowship. The authors are grateful to Berhampur University for infrastructure. We acknowledge IISER Berhampur for NMR and sample characterization facilities. The authors are thankful to Alisha Rani Tripathy and Akash Bisoyi of IISER Thiruvananthapuram for their timely help.

References

1. (a) N. N. Rao, B. B. Parida and J. K. Cha, Org. Lett., 2014, 16, 6208–6211; (b) B. B. Parida, P. P. Das, M. Niocel and J. K. Cha, Org. Lett., 2013, 15, 1780–1783; (c) B. B. Parida, I. L. Lysenko and J. K. Cha, Org. Lett., 2012, 14, 6258–6261.
2. (a) S. Chandrasekhar, B. B. Parida and C. Rambabu, J. Org. Chem., 2008, 73, 7826–7828; (b) B. P. Raiguru, J. Panda, S. Mohapatra and S. Nayak, J. Mol. Struct., 2023, 1294, 136282.
3. (a) S. S. Acharya, S. Patra, R. Maharana, M. Dash, L. M. Barad and B. B. Parida, Org. Biomol. Chem., 2024, 22, 2916–2947; (b) A. Saha, M. Shankar, S. Sau and A. K. Sahoo, Chem. Commun., 2022, 58, 4561–4587; (c) S. S. Panda and N. K. Sharma, Org. Biomol. Chem., 2023, 21, 1468–1477.
4. A. Biffis, P. Centomo, A. D. Zottom and M. Zecca, Chem. Rev., 2018, 118, 2249–2295.
5. (a) T. Niwa, Y. Uetake, M. Isoda, T. Takimoto, M. Nakaoka, D. Hashizume, H. Sakurai and T. Hosoya, Nat. Catal., 2021, 4, 1080–1088; (b) I. Hussain, J. Capricho and M. A. Yawer, Adv. Synth. Catal., 2016, 358, 3320–3349; (c) S. E. Hooshmand, B. Heidari, R. Sedghi and R. S. Varma, Green Chem., 2019, 21, 381–405; (d) A. Hassan, A. S. Baghel, A. Kumar and N. Das, Chem.–Asian J., 2023, e202300778; (e) S. S. Acharya and B. B. Parida, ChemistrySelect, 2024, 9, e202305233.
6. (a) S. Yuan, J. Chang and B. Yu, Top. Curr. Chem., 2020, 23, 378,  DOI:10.1007/s41061-020-0285-9; (b) S. S. Acharya, S. Patra, L. M. Barad, A. Roul and B. B. Parida, New J. Chem., 2024, 48, 7614–7638; (c) M. C. Kozlowski, B. J. Morgan and E. C. Linton, Chem. Soc. Rev., 2009, 38, 3193–3207; (d) G. Bringmann, T. Gulder, T. A. M. Gulder and M. Breuning, Chem. Rev., 2011, 111, 563–639; (e) G. Bringmann, T. Pabst, P. Henschel, J. Kraus, K. Peters, E.-M. Peters, D. S. Rycroft and J. D. Connolly, J. Am. Chem. Soc., 2000, 122, 9127–9133.
7. (a) J. Wencel-Delord, A. Panossian, F. R. Leroux and F. Colobert, Chem. Soc. Rev., 2015, 44, 3418–3430; (b) J. A. Ashenhurst, Chem. Soc. Rev., 2009, 39, 540–548.
8. P. Wu, T. E. Nielsen and M. H. Clausen, Drug Discovery Today, 2016, 21, 5–10.
9. (a) Y. Zhu, W. Dong and W. Tang, Adv. Agrochem, 2022, 1, 125–138; (b) P. Devendar, R.-Y. Qu, W.-M. Kang, B. He and G.-F. Yang, J. Agric. Food Chem., 2018, 66, 8914–8934.
10. (a) Z.-R. Li, F.-Z. Suo, B. Hu, Y.-J. Guo, D.-J. Fu, B. Yu, Y.-C. Zheng and H.-M. Liu, Bioorg. Chem., 2019, 84, 164–169; (b) C. N. Johnson, D. A. Erlanson, C. W. Murray and D. C. Rees, J. Med. Chem., 2017, 60, 89–99; (c) Y. Duan, Y. Guan, W. Qin, X. Zhai, B. Yu and H. Liu, MedChemComm, 2018, 9, 1779–1802; (d) B. Yu, X.-J. Shi, Y.-F. Zheng, Y. Fang, E. Zhang, D.-Q. Yu and H.-M. Liu, Eur. J. Med. Chem., 2013, 69, 323–330.
11. (a) R. S. Varma, ACS Sustainable Chem. Eng., 2016, 4, 5866–5878; (b) R. A. Sheldon, Chem. Soc. Rev., 2012, 41, 1437–1451; (c) L. L. Chng, N. Erathodiyil and J. Y. Ying, Acc. Chem. Res., 2013, 46, 1825–1837; (d) H. Ahmad and M. K. Hossain, Mater. Adv., 2022, 3, 859–887.
12. (a) A. Balanta, C. Godard and C. Claver, Chem. Soc. Rev., 2011, 40, 4973–4985; (b) A. Fihri, M. Bouhrara, B. Nekoueishahraki, J.-M. Basset and V. Polshettiwar, Chem. Soc. Rev., 2011, 40, 5181–5203; (c) R. Narayanan, Molecules, 2010, 15, 2124–2138; (d) C. K. Pal, A. K. Jena, D. Das, S. Sahu and R. K. Singh, ChemistrySelect, 2021, 6, 7944–7949.
13. P. Du, R. An, Y. Liang, P. Lei and H. Zhang, Coord. Chem. Rev., 2022, 471, 214745.
14. Z. Zhang, Q. Han, J. W. Lau and B. Xing, ACS Mater. Lett., 2020, 2, 1516–1531.
15. S. Y. Lee, M. Lin, A. Lee and Y. I. Park, Nanomaterials, 2017, 7, 411.
16. (a) S. Moradi, J. Safari and M. Moradian, ChemistrySelect, 2024, 9, e202302750; (b) M. Daraie, M. Mirzaei, M. Bazargan, V. S. Amiri, B. A. Sanati and M. M. Heravi, Sci. Rep., 2022, 12, 12004.
17. M. U. Khan and Z. A. Siddiqui, ACS Omega, 2018, 3, 10357–10364.
18. (a) F. Ding, Y. Li, P. Yan, Y. Deng, D. Wang, Y. Zhang, I. Dragutan, V. Dragutan and K. Wang, Molecules, 2018, 23, 2435; (b) A. B. Yousaf, M. Imran, M. Farooq and P. Kasak, Sci. Rep., 2018, 8, 4354.
19. (a) S. K. Swain, G. Phaomei, S. K. Tripathy, N. Yaiphaba, R. B. Devi, S. Nayak and B. B. Parida, J. Mol. Struct., 2022, 1247, 131330; (b) S. K. Choudhury, P. Rout, B. B. Parida, J.-C. Florent, L. Johannes, G. Phaomei, E. Bertounesque and L. Rout, Eur. J. Org Chem., 2017, 5275–5292; (c) S. K. Swain, A. Sahoo, S. K. Swain, S. K. Tripathy and G. Phaomei, Dalton Trans., 2020, 49, 14605–14612; (d) L. Rout, B. B. Parida, J.-C. Florent, L. Johannes, S. K. Choudhury, G. Phaomei, J. Scanlon and E. Bertounesque, Chem.–Eur. J., 2016, 22, 14812–14815.
20. E. Ghonchepour, M. R. Islami and A. M. Tikadri, J. Organomet. Chem., 2019, 883, 1–10.
21. N. Y. Baran, T. Baran, M. Nasrollahzadeh and R. S. Varma, J. Organomet. Chem., 2019, 900, 120916.
22. T. Yamada, H. Masuda, K. Park, T. Tachikawa, N. Ito, T. Ichikawa, M. Yoshimura, Y. Takagi, Y. Sawama, Y. Ohya and H. Sajiki, Catalysts, 2019, 9, 461.
23. Y. Dong, F. Xue and Y. Wei, J. Phys. Chem. Solids, 2021, 153, 110007.
24. R. K. Sharma, M. Yadav, R. Gaur, Y. Monga and A. Adholeya, Catal. Sci. Technol., 2015, 5, 2728–2740.
25. T. Baran, Carbohydr. Polym., 2018, 195, 45–52.
26. A. Khazaei, M. Khazaei and M. Nasrollahzadeh, Tetrahedron, 2017, 73, 5624–5633.
27. K. Zheng, C. Shen, J. Qiao, J. Tong, J. Jin and P. Zhang, Catalysts, 2018, 8, 443.
28. N. Razavi, B. Akhlaghinia and R. Jahanshahi, Catal. Lett., 2017, 147, 360–373.
29. A. Mohhammadinezhad and B. Akhlaghinia, Green Chem., 2017, 19, 5625–5641.
30. P. Moradi and M. Hajjami, RSC Adv., 2021, 11, 25867–25879.
31. B. Lakshminarayana, J. Chakraborty, G. Satyanarayana and C. Subrahmanyam, RSC Adv., 2018, 8, 21030–21039.
32. M. Nikoorazm, A. G. Choghamarani, M. Ghobadi and S. Massahi, Appl. Organomet. Chem., 2017, e3848.
33. M. Gholinejad, F. Zareh and C. Najera, Appl. Organomet. Chem., 2018, 32, e3984.
34. F. Masing, H. Nusse, J. Klingauf and A. Studer, Org. Lett., 2018, 20, 752–755.

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Footnotes

† The manuscript is dedicated to 70th Birth Anniversary of Prof. Satyaban Jena (Former Professor, Department of Chemistry, Utkal University, Odisha).

‡ Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d4ra00686k

§ Equal contribution in the work.

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