J. Serb. Chem. Soc.

70 (89)10571066 (2005) JSCS 3343

UDC 536.7:547.79+547.466+546.732,742 Original scientific paper

Thermodynamics of binary and ternary complexes of 3-amino-1,2,4-triazole and amino acids with Ni(II) and Co(II) metal ions
AYE ERA, TUBA IMANOLU* and SHEYLA PURA Istanbul University, Engineering Faculty, Department of Chemistry, Avcilar 34850, Istanbul, Turkey (e-mail: tusase@istanbul.edu.tr) (Received 22 June, revised 24 November 2004) Abstract: The stability constants of the 1:1 binary complexes of Ni(II) and Co(II) with 3-amino-1,2,4-triazole (AT), leucine (Leu) and glutamic acid (Glu), and the 1:1:1 ternary complex of them and the protonation constants of the ligands were determined potentiometrically at a constant ionic strength of I = 0.10 mol L-1 (NaClO4) in aqueous solutions at 15.0 and 25.0 C. The thermodynamic parameters DGf0, DHf0 and DSf0 are reported for the formation reactions of the complexes. The enthalpy changes of all the complexations were found to be negative but the entropy changes positive. While the driving force for the formation of the Ni(II), Co(II) AT complexes is the enthalpy decrease, the driving force for the ternary complexes of AT is the entropy increase. Keywords: leucine, glutamic acid, amitrole, binary and ternary complexes. INTRODUCTION

2-Amino-4-methylpentanoic acid, leucine (Leu), and 2-aminoglutaric acid, glutamic acid (Glu), are very important bioligands for the health of humans and animals. Leu, an exogenous amino acid including one carboxyl group and one amino group, exists in several proteins. Glu is an endogenous amino acid which is found in several vegetable proteins, such as wheat, corn, soya, etc. It has two carboxyl groups and one amino group. Both amino acids form stabile complexes with metal ions through their carboxyl and amino groups.1 The structures of both amino acids are shown in Scheme 1. Amino acids have been used as primary ligands and a large amount of research concerning metal amino acid complexation has been reported.2 Every free amino acid has at least two pKa values: the one associated with the protonation of the carboxylate and the other associated with the deprotonation of the amine group. Amino acids in which the side-chain itself contains an ionizable group have a third pKa value, the one associated with protonation or deprotonation
* Author for correspondence

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in the side chain. The pKa values of Glu and Leu are given in Table I.3
TABLE I. pKa values of Glu and Leu Amino acid Leucine Glutamic acid a-COO 2.3 2.1 a-NH3 9.7 9.5 4.1 Side chain

The protonation constants of Leu and Glu are shown in Scheme 1.

Scheme 1.

Glu and Leu coordinate metals via their amino and carboxyl groups,1 as can be seen an Scheme 2.

Scheme 2.

3-Amino-1,2,4-triazole, amitrole (AT), is commonly known as a herbicide and it has fungicide activity.4,5 AT is adsorbed on soil particles and organic matter by proton association. It has been found to cause cancer of the thyroid in rats and mice. AT is also of interest as a ligand which forms complexes both in aqueous solution and in the solid state. It has at least two donor centers available for coordination. Coordination compounds of AT with some transition metals were investigated previously in aqueous solution by the pH-metric method and electronic spectroscopy.68 The stability constants of the binary complexes of AT with Ni and Co were investigated by Gabryzewski who reported log b1 = 1.4; log b2 = 3.40; log b3 = 4.54; log b1 = 2.34; log b2 = 5.81 and log b3 = 6.95, for AT-Co and AT-Ni, respectively.7 AT is a basic compound that is able to protonate in aqueous solutions depending on the pH, since the pKa is 4.14.9 The structures of AT and AT coordinated to metal ions through the amino group and nitrogen atoms in the triazole ring are shown in Scheme 3. In recent years, there have been no reports of studies of ternary complexes of AT with the amino acids in the literature.

Ni(II) AND Co(II) COMPLEXES

1059

Scheme 3.

In this work, the stability constants and thermodynamic parameters of binary and ternary complexes of Ni2+ and Co2+ with AT, Leu and Glu were determined from data from potentiometric pH titrations in aqueous solution at 15.0 and 25.0 C. Measurement of pH is an accurate technique which can be used for studying complexes and ionic equilibria.10 The Irving-Rossotti treatment11,12 was used to evaluate the stability constants of the complexes formed between the metal ions and AT in the absence and the presence of some amino acids, such as glutamic acid and L-leucine.
EXPERIMENTAL Materials Leucine (Leu), glutamic acid (Glu), the nitrate salts of nickel and cobalt, sodium perchlorate, perchloric acid, sodium hydroxide (titrisol) were from Merck. All reagents were of analytical grade. Amitrole (AT) of high purity was obtained from Fluka and was used after recrystallization from ethanol. Analytical methods Potentiometric measurement were performed using a TitroLine alpha Schott pH-meter accurate to 0.001 pH units at 25 0.1 C with a Schott Blue line combined glasscalomel electrode. The accuracy of the pH-meter was controlled using standard buffer solutions with pH values of 4.00, 7.00 and 9.00 at 25 0.1 C. Stock solutions of the metal ions, AT, Glu and Leu were prepared in doubly distilled water and the required concentration was obtained by a suitable dilution. The ionic strength of the solutions was maintained constant at 0.1 mol L-1 by addition of the appropriate amount of 1.0 mol L-1 NaClO4 stock solution. Measurements The experimental procedure involved the potentiometric titrations of the following solutions: a) HClO4 (1.0 10-2 mol L-1) b) HClO4 (1.0 10-2 mol L-1) + AT (2.0 10-3 mol L-1) c) HClO4 (1.0 10-2 mol L-1) + AT (2.0 10-3 mol L-1) + Metal (2.0 10-3 mol L-1) d) HClO4 (1.0 10-2 mol L-1) + Glu (2.0 10-3 mol L-1) e) HClO4 (1.0 10-2 mol L-1) + Glu (2.0 10-3 mol L-1) + Metal (2.0 10-3 mol L-1) f) HClO4 (1.0 10-2 mol L-1) + Leu (2.0 10-3 mol L-1) g) HClO4 (1.0 10-2 mol L-1) + Leu (2.0 10-3 mol L-1) + Metal (2.0 10-3 mol L-1) h) HClO4 (1.0 10-2 mol L-1) + AT (2.0 10-3 mol L-1) + Glu (2.0 10-3 mol L-1) j) HClO4 (1.0 10-2 mol L-1) + AT (2.0 10-3 mol L-1) + Leu (2.0 10-3 mol L-1) k) HClO4 (1.0 10-2 mol L-1) + AT (2.0 10-3 mol L-1) + Glu (2.0 10-3 mol L-1) + Metal (2.0 10-3 mol L-1)

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l) HClO4 (1.0 10-2 mol L-1) + AT (2.0 10-3 mol L-1) + Leu (2.0 10-3 mol L-1) + Metal (2.0 10-3 mol L-1). At least five replicate titrations were performed for each solution. Prepurified nitrogen was bubbled through the experimental solution in the cell. Then the hydrogen ion concentration was determined by a number of successive readings of the pH meter. Increments of standard NaOH (titrisol Merck) were added from an automatic burette and the equilibrium pH values were measured until they reached 2.0 to 11.0. Titration curves were constructed by plotting the pH values as a function of mL added of NaOH followed by the appropriate mathematical treatments of the data. Calculations The protonation constants of the ligands were calculated from the data of the potentiometric pH titrations of solutions (a), (b), (d) and (f). For this purpose, the average proton-ligand formation number, nA, at various pH for the ligands were determined from the following equation.13,14 nA = y + (u1 - u 2 )([ B ] + [ A ]0 ) (V0 + u1)[ L ]0 (1)

where: [B] / mol L-1 is the concentration of NaOH titrisol = 1.0 10-1; [A]0 / mol L-1 is the initial concentration of HClO4 solution = 1.0 10-2; [L]0 / mol L-1 is the total ligand concentration = 2.0 10-3; V0 / mL is the volume of solution to be titrated = 25.0; u1 and u2/mL are the volumes of NaOH required for the perchloric acid and the ligand titration curves at a given pH and y is the number of dissociable protons of the ligand. The values of pKa, pK2a, ... were calculated from the nA = f(pH) relationship at nA = 0.5, 1.5, ... .2 The stability constants of the binary and ternary complexes were calculated using the titrations data of solutions (a) (l), the metalligand(s) formation number, nL, at various pH values were determined from the following equation.13,14 n1 = (u 3 - u 2 )([ B ] + [ A ]0 + [ L ]0 ( y - nA ) (V0 + u 3 )nA[ M ]0 (2)

where: [M]0/mol L-1 is the total metal concentration = 2.0 10-3; nL is the average number of ligand molecules attached per metal ion; u3 is the volume of NaOH required for the ligandmetal titration curves at a given pH and the other symbols are the same as above. Then pL values were calculated using the equation:14,15 pL = log 1 + b1[ H + ] + b 2[ H + ]2 + b 3[ H + ]3 + ... [ L ]0 - nL [ M ]0 (3)

where: pL is the free ligand exponent; b1 = KHHL, b2 = KHHL KHLH2L, b3 = KHHL KHLH2L KH2LH3L. Having thus obtained the corresponding values of nL and pL, the formation curve of the metalligand(s) system is drawn and the stability constant is calculated at nL = 0.5.15 All the calculations were done using a 450 MHz micro processor Pentium III personal computer and the Microsoft Excel 2000 program. Assuming that DH0f is constant in the studied range of temperatures, the DH0f values were calculated from the stability constants according to the well known equations. ln 0 K 2 DH f T2 - T1 = K1 R T2T1 DG 0 = - RT ln K f DG 0 = DH 0 - T DS 0 f f f (4)

(5) (6)

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RESULTS AND DISCUSSION

Protonligand systems The potentiometric titration curves of the ligands at 25.0 C are shown in Figs. 13. Similar titration curves were obtained at the other studied temperatures. As expected and previously reported, each curve exhibits an extremely sharp inflection at the point corresponding to the concentration of the protons dissociated: Glu gives two, Leu gives one and AT no proton (in reality protonated AT gives one proton). The protonation steps of the Glu systems are described as follows: L + H K HL K1 = [HL]/[H][L] 1 HL + H H2 L + H
K2
K3

H2 L H3 L

K2 = [H2L]/[H][HL] K3 = [H3L]/[H][H2L]

In this formulation, the equilibria are described as protonation reactions to give protonated amino acids and accordingly the equilibrium constants are stability constants. As is apparent from these equations, K1, K2 and K3 are equal to the reciprocal of the respective acid dissociation constants (Ka). Protonation of the amino or carboxyl groups means that the nature of the amino acid in solution is pH dependent, HOOCCH2CH2 CH COOH HOOC CH2CH2 CH COO NH + 3 Glu pH < 2 OOCCH CH CH COO 2 2 NH + 3 pH < 7 (log K2) H3C CH CH2 CH COOH CH3 NH + 3 Leu pH < 2 H3C CH CH2 CH COO CH3 pH > 9 (log K3) Protonated AT: NH2 NH + 3 pH < 3 (log K3) OOCCH CH CH COO 2 2 NH 2 pH > 9 (log K1) H3C CH CH2 CH COO CH3 NH + 3 pH < 3 (log K2)

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The determined values of the protonation constants and the thermodynamic parameters are given in Tables II and III. As can be seen in Table II, the protonation constants of the ligands decreased with increasing temperature. Table III shows the exothermic behavior of the proton exchange reaction, meaning that the protonation enthalpy is negative with a high absolute value.
TABLE II. Log protonation constants for the ligands at I = 0.10 mol L-1 (NaClO4) Ligands log K3 ([H3L]/[H] [H2L]) Glu log K2 ([H2L]/[H] [HL]) log K1 ([HL]/[H] [L]) Leu AT log K2 ([H2L]/[H] [HL]) log K1 ([HL]/[H] [L]) log K1 ([HL]/[H] [L]) T = 15.0 C 4.25 0.01 9.66 0.05 9.66 0.06 3.80 0.01 T = 25.0 C 4.18 0.02 9.51 0.04 9.54 0.02 3.72 0.01

TABLE III. Thermodynamic parameters for the protonligand systems Ligands Glu Leu AT log K2 log K1 log K1 log K1 DHf0 / kJ mol-1 (15.025.0 C) 25 10 20 13 DGf0 / kJ mol-1 (25.0 C) 54 24 55 21 DSf0 / J mol-1 K-1 (25.0 C) 99 47 116 27

The DHf0 values are accurate to 13 kJ mol-1 and the DSf0 values to 45 J K-1 mol-1

According to the HSAB classification,17 the ligands can be arranged as shown in Scheme 4.
Hard Glu, Leu (O donor) Medium Glu, Leu (N donor) AT (N donor) Soft All three ligands are of relative softness due to the N donor

Scheme 4. The contributions of the enthalpy part of the ligands Glu and Leu to the free energy decrease are about 3646 %. However, the AT ligand has an enthalpy change which contributes 62 % to the free energy decrease. In aqueous solution, Glu and Leu behave as hard ligands with a preference of O donation (entropy-controlled), whereas AT has an enthalpy-controlled soft ligand character due to the N donor atom.16

Binary complex systems The potentiometric titration curves of NiAT, NiGlu and NiLeu systems at 25.0 C are also shown in Figs. 13. Similar titration curves were obtained at the other studied temperatures and metal ions. The stability constants of the 1:1 binary

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Fig. 2. Potentiometric titration curves of () Fig. 1. Potentimetric titration curves of () HClO4, () HClO4+AT, () HClO4+AT+Ni2+ HClO4, () HClO4+Glu, () HClO4+Glu+Ni2+ solutions. solutions.

Fig. 3. Potentiometric titration curves of () HClO4, () HClO4+Leu, () HClO4+Leu+Ni2+ solutions.

complexes of Glu, Leu and AT with the metal ions were calculated using the Irving-Rossotti method. To evaluate the formation constant of the formed complexes, the values of nL and pL are needed at different pH values. According to Irving-Rossotti,12 the values of nL and pL were caclulated and the experimental formation curves were constructed by plotting nL vs. pL. The resulting values are shown in Table IV. Also the thermodynamic parameters, presented in Table V, were computed using Eqs. (4) (6). From Table IV it can be seen that the stability constants of the binary Ni2+ and Co2+ complexes with each of the ligands decrease with increasing temperature; and that the complexation is exothermic. According to HSAB classification, metals can be arranged as hard Ni2+ (relatively) Co2+ (relatively), medium Ni2+, Co2+, soft Ni2+ (relatively) Co2+ (relatively). In Table IV, it can be seen that the stability constants of the binary Ni2+ complexes with the ligands are greater that those of Co2+, which can be described in terms of an

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Irwing-Williams series.16 The log K values should indicate a Co2+ < Ni2+ order, when the charge/ion radius ratios of the metal ions upon coordination with oxygen or nitrogen atoms in the ligand are considered. The reaction temperatures of the complexes are higher the greater the charge/radius ratio is, as can be seen in Table V. The table shows that the major driving force of the binary complexation reactions with Glu and Leu ligands is entropy-controlled, while it is enthalpy-controlled in the complexes with the AT ligand. When the entropy values are considered, Glu and Leu ligands are hard acceptors induced by oxygen donation, hence both the ligands and the metal ions are surrounded by water molecules. On the one hand, the formation of binary complexes with these structures requires a great deal of energy to break the additional bonds, resulting in greater entropy values. On the other hand, the AT binary systems show entropy values as small as 2 J mol1 K1, which is indicative of a) the soft acceptor behavior of the metal ions against a relative donor, namely nitrogen; and b) the relative scarcity of metal ionwater and ligandwater bonds.
TABLE IV. 1:1 Stability constants of the binary complexes at I = 0.10 mol L-1 (NaClO4) System GluNi2+ GluCo2+ LeuNi2+ LeuCo2+ ATNi2+ ATCo2+ * Reference 18 TABLE V. 1:1 Thermodynamic parameters of the binary systems System GluNi2+ GluCo2+ LeuNi2+ LeuCo2+ ATNi2+ ATCo2+ The DHf
0 values are

T = 15.0 C log KNiNiGlu log log log KCo KNi KCo

CoGlu

T = 25.0 C 5.87 0.01 4.68 0.01 5.60 0.01 4.30 0.04 3.05 0.03 3.00 0.01

log K1 5.90* 5.06* 5.58* 4.49*

5.92 0.01 4.74 0.02 5.67 0.03 4.38 0.01 3.12 0.02 3.10 0.05

NiLeu

CoLeu log KNiNiAT log KCoCoAT

DHf0/kJ mol-1 (15.025.0 C) log KMMA1 log log KM KM

MA1

DGf0/kJ mol-1 (25.0 C) 34 27 32 25 17 17

DSf0/J mol-1 K-1 (25.0 C) 85 56 74 44 20 2.0

8 10 10 12 12 16 and the DSf

log KMMA2 log log

MA2 KMML KMML

accurate

to 1 kJ mol-1

0 values to 3 J K-1 mol-1

Ternary complex system The potentiometric titration curves for NiATGlu and NiATLeu in a 1:1:1 molar ratio at 25.0 C are shown in Figs. 4 and 5 respectively. Similar titration curves were obtained at the other studied temperatures and metal ion. From Table

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Fig. 4. Potentiometric titration curves of () HClO4, () HClO4+Glu+AT, () HClO4+Glu+AT+Ni2+ solutions.

Fig. 5. Potentiometric titration curves of () HClO4, () HClO4+Leu+AT, () HClO4+Leu+AT+Ni2+ solutions.

IV, it can be seen that log KM(Glu) and log KM(Leu) are greater than log KM(AT). Therefore, M(II) will be chelated by an amino acid in prefence to AT and it is reasonable to assume that the predominate initial step in the formation of mixed chelates must be the coordination of AT by M(II)Glu and M(II)Leu. The following equilibria were assumed for the ternary complexes of the AT systems: M(II) + Hn(amino acid) M(amino acid) + nH+ M(amino acid) + AT M(amino acid)(AT)
TABLE VI. Stability constants of the 1:1:1 ternary complexes at I = 0.10 mol L-1 (NaClO4) System ATGluNi2+ ATGluCo2+ ATLeuNi2+ ATLeuCo2+ log log log log KNiGlu KCoGlu KNiLeu KCoLeu
NiGluAT CoGluAT NiLeuAT CoLeuAT

T = 15.0 C 6.50 0.02 4.62 0.01 6.79 0.01 5.12 0.01

T = 25.0 C 6.43 0.01 4.55 0.03 6.72 0.01 5.04 0.05

TABLE VII. 1:1:1 Thermodynamic parameters of the ternary systems System ATGluNi2+ ATGluCo2+ ATLeuNi2+ ATLeuCo2+ log KMA1MA1L log KMA1MA1L log log KMA2 KMA2
MA2L MA2L

DHf0 / kJ mol-1 (15.025.0 C) 12 12 10 12

DGf0 / kJ mol-1 (25.0 C) 37 26 38 38

DSf0 / J mol-1 K-1 (25.0 C) 84 48 96 90

The DHf0 values are accurate to 12 kJ mol-1 and the DSf0 values to 34 J K-1 mol-1

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The stability constants of the 1:1:1 ternary complexes of AT, Glu and Leu with the metals were calculated from Eqs. (2) and (3). Using the half-value method11,12 and least squares fits, the stability constant values were determined and are listed in Table VI. Also, the thermodynamic parameters, presented in Table VII, were computed from Eqs. (4)(6). From Table VI, it can be seen that with increasing temperature, the stability constants of all the ternary complexes decrease. Table VII shows that the major driving force of the ternary complex series with both metal ions is entropically supported. In the ternary complexes, both the acceptors (metal ions) and donors (ligand) have a hard nature and the metalligand bonds are considered to be rather electrostatic (ionic).16
IZVOD

TERMODINAMIKA BINARNIH I TERNERNIH KOMPLEKSA 3-AMINO-1,2,4-TRIAZOLA I AMINOKISELINA SA JONIMA Ni(II) i Co(II)

AYE ERA, TUBA IMANOLU i SHEYLA PURA Istanbul University, Engineering Faculty, Department of Chemistry, Avcilar 34850, Istanbul, Turkey

Potenciometrijski su odre|ene konstante stabilnosti na 15,0 i 25,0 C i jonskoj ja~ini I = 0,10 mol L-1 (NaClO4) za 1:1 binarne komplekse Ni(II) i Co(II) sa 3-amino-1,2,4-triazolom (AT), leucinom (Leu) i glutaminskom kiselinom (Glu) i wihove 1:1:1 ternerne komplekse, kao i konstante protonacije liganada. Odre|eni su termodinami~ki parametri za stvarawe ovih kompleksa, DGf0, DHf0 i DSf0. Na|eno je da su sve standardne entalpije stvarawa negativne, dok su sve standardne entropije stvarawa pozitivne. Dok su pogonske sile stvarawa Ni(II) i Co(II) AT kompleksa smawewe entalpije reakcija, kod ternernih kompleksa sa AT to je enetropije.
(Primqeno 22. juna, revidirano 24. novembra 2004)

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