Abstract
Four tridentate ligands L1-L4, namely N,N-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl) pyridin-2-amine: L1, 5-chloro-N,N-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl) pyridin-2-amine:L2, N,N-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)thiazol-2-amine:L3 and N,N-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-6-methylpyridin-2-amine: L4 were synthesized, characterized (by13C NMR, 1H NMR and mass spectroscopy) and employed for the synthesis of copper(II) complexes in situ. These ligands contain three sp2 nitrogen atoms, two pyrazole nitrogen and one pyridine nitrogen, capable of coordinating with copper (II). Then the catalytic properties of certain complexes formed in situ were evaluated to catalyze the oxidation of catechol to o-quinone. Among these complexes, the L1/Cu(CH3COO)2 complex which showed good catalytic activity of the combination 1:1 ligand/metal in THF for this reaction, with a reaction rate of oxidation of catechol to o-quinone equal to 26.37 μmol L−1 min−1.
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Introduction
The synthesis of multidentate heterocyclic ligands which have donor atoms such as nitrogen and oxygen are of considerable biological interest and their resulting metal complexes. Most of the mulidentate ligands are prepared for the purpose of mimicking the behavior of various metalloproteins, such as copper-containing proteins, hemocyanin, and tyrosinase [1,2,3,4,5]. Great efforts have been made to mimic tyrosinase activity using copper complexes coordinated to multidentate heterocyclic ligands based on pyrazole. Different types of catechol have been used in the literature as models for this type of study [6,7,8,9] (Scheme 1).
Oxidation of catechol to o-quinone
Much information regarding the role of transition metals in oxidative and hydrolytic dinuclear metalloenzymes, such as catechol oxidases, has been obtained from comparative studies of metalloenzymes and synthetic model metal complexes [10,11,12,13,14,15,16]. Studies with model complexes have been described, aiming to mimic the structural and/or functional properties of these metalloenzymes with the presence of labile sites essential for the binding of the substrate and/or nucleophiles available to initiate the catalytic process [17,18,19], and role of the electronegative atom present on the ligand backbone and the mode of binding of the substrate on the catecholase type activities of the complexes [20]. Heterocyclic compounds based on pyrazole have also occupied an important place in modern chemistry due to their various applications in many fields such as catalysis [21,22,23,24,25], pharmacology [26, 27], complexation [28,29,30], electronics [31], corrosion inhibitor [32], cytotoxic activities [33], transport of lithium cations [34], extraction of lithium and cesium cations [35, 36] antifungal and antibacterial activities [37, 38]. Considerable studies focus on the synthesis of complexes with nitrogen ligands designed to model catecholase [39,40,41,42,43,44,45,46,47]. Catalytic activity has been studied as complexes formed in situ [48, 49] or as isolated complexes [50, 51]. This study reveals that the complex formed from the L2/CuCl2 combination in THF shows a higher activity towards the other ligand/copper(II) combinations, with a rate Vmax equal to 16.03 μmol L−1 min−1 and a low value of Km equal to 0.018 mol L−1. In the continuity of laboratory work in this field [21, 48, 49, 52,53,54,55], the ligands L1–L4 based on pyrazole and pyridine were examined for the catecholasic activities formed with different copper(II) salts Cu(CH3COO)2, CuSO4, Cu(NO3)2 and CuCl2, and the effect of ligand concentration, the nature of the ligand, the nature of the counter-anion and the nature of the solvent were studied (MeOH and THF).
In this work, we report the synthesis and caracterisation of the ligands L1-L4, then, we study the catalytic activity of the ligand/copper(II) complex formed in situ of the oxidation of catechol to o-quinone.
Materials and methods
Materials
The (3,5-dimethyl-1H-pyrazol-1-yl) methanol has been prepared according to the literature [56, 57]. Solvents (methanol and THF,) and all other reagents (catechol, anhydrous copper salts Cu(CH3COO)2, CuSO4, Cu(NO3)2 and CuCl2) were purchased from Aldrich and were used as received without further purification.
Physical measurements
Nuclear magnetic resonance (NMR) spectra were recorded using a Bruker-400 instruments operating at 400 MHz for 1H spectra and 101 MHz for 13C spectra. Mass spectra were obtained using the electrospray ionization (ESI) technique and UV–Vis measurements were spectrophotometrically made using a Shimadzu UV-1800 spectrophotometer at 25 °C.
Synthesis of the ligands
The heterocyclic ligands L1–L4 [58, 59] (Scheme 2) where prepared by reaction between two equivalents of 1-hydroxymethyl-3,5-dimethylpyrazole or 1-hydroxymethylpyrazole and one equivalents of corresponding primary amine under reflux (60 °C) for 6 h under magnetic stirring in acetonitrile, then the solution is dried over MgSO4, filtered and then concentrated in a rotary evaporator. The product obtained was extracted with CH2Cl2/H2O.
Structure of prepared tripodal ligands L1-L4
Catecholase activity measurements
Kinetic measurements were spectrophotometrically made using à Shimadzu UV-1800 PC spectrophotometer, following the appearance of o-quinone over time at 25 °C (390 nm absorbance maximum, ε = 1600 L mol−1 cm−1 in methanol, ε = 1900 L mol−1 cm−1 in THF). The complexes are formed in situ, by mixing successively 0.15 mL of a solution (2 × 10−3 mol L−1) of metals salts with 0.15 mL of ligand solution (2 × 10−3 mol L−1), complexes formed in situ were treated with 2 mL (0.10 mol L−1) of catechol in methanol (MeOH) or tetrahydrofuran (THF) under aerobic conditions.
Results and discussion
Characterisation of ligands
The ligands L1-L4 used in this study are obtained with good yields and characterized by different identification methods such as 1H NMR, 13C NMR and mass spectroscopy.
N,N-Bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)pyridin-2-amine: L1
White solid, Yield: 72%, Melting point: 100–104 °C. 1H NMR (400 MHz, CDCl3) δ 8.24–6.68 (m, 4H, CHpy), 5.93–5.83 (m, 2H, CHpz), 5.61–5.22 (s, 4H, CH2), 2.54–2.18 (s, 12H, CH3). 13C NMR (101 MHz, CDCl3) δ 155.00 (C=Npy), 148.49 (C-Npy), 147.20 (C=Npz), 139.98 (C-Npz), 137.87 (Cpy,para), 114.99 (Cpy,meta- left), 113.85 (Cpy,meta- right), 106.21 (CHpz), 70.31 (CH2), 13.10 (CH3–C=N), 10.68 (CH3-C-N). m/z: calcd 310.19 found 311.1 [M + 1].
5-chloro-N,N-Bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)pyridin-2-amine: L2
White solid, Yield: 72%, Melting point: 176–180 °C. 1H NMR (400 MHz, CDCl3) δ 8.05–7.97 (m, 1H, CH-Npy), 7.42 (dt, J = 8.8, 2.2 Hz, 1H, CH–CCl), 6.69 (d, J = 8.8 Hz, 1H, CH–C=Npy), 6.09–5.91 (m, 2H, CHpz), 5.83–5.17 (s, 4H, CH2), 3.01–1.58 (s, 12H, CH3). 13C NMR (101 MHz, CDCl3) δ 153.94 (C=Npy), 146.27 (CH-Npy), 145.15(C=Npz), 143.23 (Cpz–N), 137.91 (CH–CCl), 122.07 (C–Cl), 111.09 (CH–C=Npy), 106.17 (CHpz), 54.55 (CH2), 12.09 (CH3–C=N), 11.24 (CH3-C-N). m/z: calcd 344.15 found 345.1 [M + 1].
N,N-Bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)thiazol-2-amine [58]: L3
Yellow solid, Yield: 72%, Melting point: 120–124 °C. 1H NMR (400 MHz, CDCl3) δ: 7.22 (d, J = 3.6 Hz, 1H, CH–S), 6.69–6.54 (m, 1H, CHC–S), 6.00–5.56 (s, 4H, CH2), 5.32 (d, J = 106.1 Hz, 2H, CHpz), 2.50–2.16 (s, 12H, CH3). 13C NMR (101 MHz, CDCl3) δ: 168.16(N=C–S), 144.37(C=Npz), 139.02(Cpz–N), 135.86(CHC–S), 109.01(CH–S), 105.40(CHpz), 70.43 (CH2), 13.08 (CH3–C=N), 11.49 (CH3–C–N). m/z: calcd 316.15 found 317.1 [M + 1].
N,N-Bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-6-methylpyridin-2-amine [59]: L4
White solid, Yield: 72%, Melting point: 118–122 °C. 1H NMR (400 MHz, CDCl3) δ 7.49–7.36 (m, 1H, CHpy,para), 6.76 (dd, J = 14.6, 8.4 Hz, 1H, CHpy-meta,right), 6.57 (dd, J = 16.8, 7.6 Hz, 1H, CHpy-meta,left), 5.94–5.77 (m, 2H, CHpz), 5.71–5.24 (s, 4H, CH2), 2.52–2.16 (s, 15H, CH3). 13C NMR (101 MHz, CDCl3) δ 155.49 CpyCH3, 153.02 C=Npy, 148.16 (C=Npz), 140.04 (Cpz–N), 138.14 (CHpy,para), 114.39 (CHpy-meta,right), 113.39 (CHpy-meta,left), 105.74 (CHpz), 54.57 (CH2), 22.54 CH3py, 13.46 (CH3–C=N), 11.41 (CH3–C–N). m/z: calcd 324.21 found 325.1 [M + 1].
Catecholase studies
In this work, we have carried out the study of the oxidation activity of the catechol to o-quinone by ligands L1-L4 with different copper(II) salts Cu(CH3COO)2, CuSO4, Cu(NO3)2 and CuCl2 in the two solvents MeOH and THF.
Catecholase studies of in situ complexes formation of ligands L 1 -L 4 in methanol
The results are summarized in Table 1 and in Figs. 1 and 2, all the complexes catalyze the oxidation reaction of catechol to o-quinone in methanol with an oxidation rate varying from a maximum of 3.52 and 2.21 μmol of substrate per liter of catalyst per min (µmol L−1 min−1) for L1/CuSO4) and L1/Cu(CH3COO)2) complexes at a low catalytic activity of 0.46 µmol L−1 min−1 for the L2/Cu(NO3)2 complex.
Absorbance evolution of o-quinone in presence of complexes formed by L1(0.15 mL) and L2 (0.15 mL) with diferent Copper salts (0.15 mL) in MeOH
Absorbance evolution of o-quinone in presence of complexes formed by L3 (0.15 mL) and L4 (0.15 mL) with diferent Copper(II) salts (0.15 mL) in MeOH
Fig. 1 and 2 show the change in absorbance as a function of time for the four anions CH3COO−, Cl−, NO3− and SO42−. Note that the absorbance in the presence of CH3COO− and NO3− anions is very high, however in the presence of Cl− and SO42− anions, the absorbance remains very low. And in the case of the L2–L4 ligands (Figs. 1 and 2), we note that the absorbance in the presence of the four anions Cl− and NO3−, SO42− and CH3COO− remains low, which does not exceed 0.1. The oxidation rates in the presence of the complexes obtained are collated in Table 1:
Catecholase studies of in situ complexes formation of ligands L 1 -L 4 in THF
We examined the catecholase activity of L1–L4 ligands with different metal salts, (Cu(CH3COO)2, CuCl2 and Cu(NO3)2 in THF on the production of o-quinone in the presence of oxygen. The oxidation rates of catechol to o-quinone and the absorbance of o-quinone as a function of time obtained are presented in Table 2 and Figs. 3 and 4.
Absorbance evolution of o-quinone in presence of complexes formed by L1 (0.15 mL) and L2 (0.15 mL) with diferent Copper(II) salts (0.15 mL) in THF
Absorbance evolution of o-quinone in presence of complexes formed by L3 (0.15 mL) and L4 (0.15 mL) with diferent Copper(II) salts (0.15 mL) in THF
As can be seen in Table 2 and Figs. 3 and 4, all the complexes catalyze the oxidation reaction of catechol to o-quinone with an oxidation rate varying from 26.37, 12.26, 11.38 to 10.21 µmol L−1 min−1 for the L1/Cu(CH3COO)2, L2/CuCl2, L4/Cu(CH3COO)2 and L2/Cu(CH3COO)2 complexes at an average oxidation rate of 4.73 µmol L−1 min−1 for the L4/CuCl2 complex.
Catecholase studies of in situ complexes formation of ligands L 1 -L 4 in methanol (1/2)
In this study, by mixing 0.1 mL of a 2 × 10–3 mol/L solution of ligand L1-L4 dissolved in methanol for analysis and 0.2 mL of a solution of the copper salt Cu(CH3COO)2, CuSO4, Cu(NO3)2 and CuCl2, and then 2 ml of a solution with a concentration of 0.10 mol/L in catechol are added. After the addition, the evolution of the absorbance at 390 nm is followed as a function of time after adjustment to zero. The evolution of the absorbance of o-quinone as a function of time is given in Figs. 5 and 6 and the rates of oxidation of catechol to o-quinone by complexes formed by ligands L1–L4 and the four salts of copper(II) obtained are collated in Table 3.
Absorbance evolution of o-quinone in presence of complexes formed by L1 (0.1 mL) and L2 (0.1 mL) with two equivalents of Copper(II) salts (0.2 mL) in MeOH
Absorbance evolution of o-quinone in presence of complexes formed by L3 (0.1 mL) and L4 (0.1 mL) with two equivalents of Copper(II) salts (0.2 mL) in MeOH
From Figs. 5 and 6 and Table 3, it is noted that the oxidation rate of catechol to o-quinone is high when using the copper complex formed by the L4 ligand and the copper(II) salt CuSO4 as a catalyst which reaches 4.24 µmol L−1 min−1 on the other hand, the oxidation rates of catechol to o-quinone remain quite low when using the complexes formed by the other ligands with the various copper(II) salts as catalysts which reach 0.44 and 0.55 µmol L−1 min−1 for combinations formed by L2/CuSO4, L3/CuSO4 and L1/CuSO4. In general, it is noted that each ligand has a special affinity with respect to the anions associated with copper.
All the complexes based on the tridentate ligands with the metal ions Cu(CH3COO)2 represent good rates of oxidation of catechol to o-quinone, on the other hand the complexes formed by the ligands L1–L4 with the other metal salts CuCl2, CuSO4 and Cu(NO3)2 which show low oxidation rates. For the same cation, we note that the oxidation rate varied from ligand to another, for example the combination formed by L1/Cu(CH3COO)2 is the best catalyst since the rate arrives at 26.37 µmol L−1 min−1 than the combinations formed by ligands L2–L4 and the same salt Cu(CH3COO)2 which reach rates of 10.21, 9.03 and 11.38 µmol L−1 min−1. Therefore, it can be concluded that the oxidation rates of catechol to o-quinone strongly depend on the nature of the tripodal ligands and the type of anion used. From Tables 1, 2, 3, it is seen that the nature of the solvent has a tremendous effect on the oxidation rates of catechols. It can be concluded that THF is the right solvent for this oxidation reaction with all the combinations formed such that the oxidation rate reaches 26.37 µmol L−1 min−1 for the L1/(Cu(CH3COO)2 combination.
Vmax and Km study
To determine the equilibrium constant Km and the maximum rate of the reaction Vmax, the Michaelis–Menten curve (Vi = f([catechol]) is used. This is done by studying the absorbance versus time for different substrate concentrations at a fixed catalyst concentration.
For this purpose, the kinetic study of five complexes was carried out: L1/Cu(CH3COO)2 (THF), L2/Cu(CH3COO)2 (THF), L3/Cu(CH3COO)2 (THF), L2/CuCl2 (THF) and L4/Cu(CH3COO)2 (THF).
This study is carried out by mixing 0.15 ml of a copper(II) salt solution with a concentration of 2 10–3 mol/L and 0.15 ml of a solution of corresponding ligands with a concentration of 2 10–3 mol/L, with 2 ml of a solution of catechol at a concentration varying from 10–3 to 0.6 mol/L in a spectrophotometric cell at room temperature and the absorbance of the o-quinone formed in the first five minutes is measured.
The initial rate of formation of o-quinone increases with the concentration of catechol, but from the concentration almost equal to 0.1 mol/L the increase The rate increase becomes low then we reach the maximum rate. The different parameters: the equilibrium constant Km and the rate Vmax of oxidation of catechol to o-quinone for the five combinations, are given in the Table 4.
According to Fig. 7, it is observed that the kinetic study for all combinations studied, that there is a good correlation between the curves found with that of the Michaelis–Menten model. The Michaelis–Menten model is applied to determine the kinetic parameters of the best catalysts to study. The rate Vmax for the different combinations in THF are high and with low Km values, which explains why the affinity is strong in THF. We give in Table 4 the initial rate found and calculated (V0 and V0calc).
Dependence of the reaction rates on the catechol concentrations varying from 10–3 to 0.6 mol/L for the oxidation reaction catalyzed by some complex formed insitu
The different parameters of the values of the rate Vmax, the equilibrium constant Km and standard deviation of the value of Vmax and Km, the coefficient of determination (R2), sum of squared deviations and the parameter correlation for the different combinations in THF are presented in the Table 5.
These different parameters were determined according to the method described by Gabar Lente [60].
UV–vis spectrophotometric study
To validate the significant catalytic activity of different combinations L1/Cu(CH3COO)2 in the THF and L1/CuSO4 in the MeOH) among the best combinations of our complexes for example, the kinetics of o-quinone and the change in absorbance was recorded every 5 min. Kinetic experiments were performed at room temperature (Fig. 8). The appearance and evolution of the intensity of a band concentrated at 390 nm, explains that the combinations are good catalysts for the oxidation of catechol to o-quinone.
Absorbance spectrum of o-quinone as a function absorption wave with time for the combination a L1/Cu(CH3COO)2 in the THF and b L1/CuSO4 in the MeOH
combination a L1/Cu(CH3COO)2 in the THF and b L1/CuSO4 in the MeOH
Conclusion
In this work, we synthesized four new tridentats ligands L1-L4, namely N,N-Bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)pyridin-2-amine:L1, 5-chloro-N,N-Bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)pyridin-2-amine: L2, N,N-Bis((3,5-dimethyl-1H-pyrazol-1-yl) methyl) thiazol-2-amine:L3 and N,N-Bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-6-methylpyridin-2-amine: L4. Moreover, we have characterized these ligands by 13C NMR, 1H NMR and mass spectroscopy. Next, we have carried out the oxidation of catechol to o-quinone by complexes formed in situ, in the presence of oxygen at room temperature; by mixing tridentate ligands based on pyrazole and pyridine with copper(II) salts. The results obtained show that all the complexes catalyze the oxidation of catechol with different oxidation rates. Finally, we studied the parameters influencing the catalytic activity of the complexes studied such as the nature and the concentration of the ligand, the nature of the metal and the anion bound to the metal, the nature of the solvent and the concentration of the catechol substrate. We also studied the kinetics of the oxidation reaction of catechol to o-quinone using the Michaelis–Menten model, to find the kinetic parameters such as Vmax and Km.
Data Availability
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References
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The authors extend their appreciation to the Deanship of Scientific Research at King Khalid University for funding this work through Large Groups Project under grant number RGP.2/226/43.
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Bouroumane, N., El Boutaybi, M., El Kodadi, M. et al. Synthesis of new heterocyclic ligands and study of the catecholase activity of catalysts based on copper(II). Reac Kinet Mech Cat 136, 1545–1562 (2023). https://doi.org/10.1007/s11144-023-02370-7
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DOI: https://doi.org/10.1007/s11144-023-02370-7