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DOI: 10.1007/s10953-015-0404-3

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Solution Equilibria and Stabilities of
Binary and Ternary Systems of Nickel(II)
Complexes with Dipicolinic Acid and the
Amino Acids (Histidine, Cysteine, Aspartic
and Glutamic Acids)
José Lema, Juseth Alejandro Ortega, José
Daniel Martínez, Mary Lorena Araujo,
Felipe Brito, Edgar Del Carpio, Lino
Hernández, et al.
Journal of Solution Chemistry

ISSN 0095-9782
Volume 44
Number 11

J Solution Chem (2015) 44:2144-2153

DOI 10.1007/s10953-015-0404-3

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 Author's personal copy
J Solution Chem (2015) 44:2144–2153
DOI 10.1007/s10953-015-0404-3

Solution Equilibria and Stabilities of Binary and Ternary

Systems of Nickel(II) Complexes with Dipicolinic Acid
and the Amino Acids (Histidine, Cysteine, Aspartic
and Glutamic Acids)

José Lema1 • Juseth Alejandro Ortega1 • José Daniel Martı́nez1 •

Mary Lorena Araujo1 • Felipe Brito1 • Edgar Del Carpio2 •

Lino Hernández2 • Vito Lubes2

Received: 7 October 2014 / Accepted: 1 July 2015 / Published online: 29 October 2015
Ó Springer Science+Business Media New York 2015

Abstract Solution equilibria in the binary systems of Ni(II)–amino acid {aspartic acid
(H2asp), glutamic acid (H2glu), cysteine (H2cys) and histidine (Hhis)} and in the ternary
systems of Ni(II)–dipicolinic acid (H2dipic)–amino acid {aspartic acid (H2asp), glutamic
acid (H2glu), cysteine (H2cys) and histidine (Hhis)} have been studied pH-potentiomet-
rically. The formation constants of the resulting mixed ligand complexes have been
determined at 25 °C and ionic strength 1.0 moldm-3 NaCl. In the Ni(II)–H2asp system the
data indicated the formation of the [NiHL]?, NiL and [NiL2]2- complexes. For the Ni(II)–
H2glu system, the formation of the species NiL and [NiL2]2- are indicated. In the Ni(II)–
H2cys system the complexes [NiHL]?, NiL and [NiHL2]- were detected, while in the
Ni(II)–Hhis system the species [NiH2L]3? [NiHL]2?, NiL?, [Ni(HL)2]2?, [NiHL2]? and
NiL2 were detected. In the ternary system Ni(II)–H2dipic–H2asp, the species
Ni(dipic)(H2L), [Ni(dipic)(HL)]-, [Ni(dipic)(L)]2- and [Ni(dipic)(L)(OH)]3- were
detected. In the Ni(II)–H2dipic–H2glu system, the species Ni(dipic)(H2L),
[Ni(dipic)(HL)]-, [Ni(dipic)(L)]2- and [Ni(dipic)(L)(OH)]3- were detected. In the Ni(II)–
H2dipic–H2cys system, the species Ni(dipic)(H2L), [Ni(dipic)(HL)]- and [Ni(dipic)(L)]2-
were detected. Finally, in the Ni(II)–H2dipic–Hhis system, the species [Ni(dipic)(L)]- and
[Ni(dipic)(L)(OH)]2- were detected. Species distribution diagrams as a function of pH are
briefly discussed.

Keywords Nickel(II) complexes  Dipicolinic acid  Potentiometric studies  Speciation 

Ternary complexes

Electronic supplementary material The online version of this article (doi:10.1007/s10953-015-0404-3)

contains supplementary material, which is available to authorized users.

& Vito Lubes

lubesv@usb.ve
1
Centro de Equilibrios en Solución, Escuela de Quı́mica, Facultad de Ciencias, Universidad Central
de Venezuela (UCV), Caracas, Venezuela
2
Departamento de Quı́mica, Universidad Simón Bolı́var (USB), Apartado 89000, Caracas 1080 A,
Venezuela

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1 Introduction

Nickel, in the form of its various alloys and compounds, is widespread and very common
in nature. It is a trace element in most plants and animals and it is essential for some
organisms. Although nickel is generally considered a highly toxic and carcinogenic metal,
microamounts of nickel are believed to be essential for human health. Estimates of the total
nickel amount in the human body fall in the range of 0.10–0.15 mgkg-1 [1].
Pyridine-2,6-dicarboxylic acid, also known as dipicolinic acid (H2dipic), is a versatile
N–O donor capable of forming stable chelates with various metal ions and can exhibit
diverse coordination modes such as bidentate, tridentate, meridian or bridging. It can
stabilize unusual oxidation states and has proven to be useful in analytical chemistry, in
corrosion inhibition and in decontamination of nuclear reactors [2].
Complexes of the first transition metals with picolinates have been studied and the
Cu(II)–picolinate system has been shown to be more active than the benchmark insuli-
nomimetic leading compounds such as the oxovanadium(IV)–picolinate complex,
VO(pa)2. Different metallopicolinate complexes have been prepared and their in vitro
insulinomimetic and in vivo antidiabetic activities were evaluated [3].
Sakurai et al. [4] studied in vivo coordination structural changes of a potent insulin-
mimetic agent, bis(picolinato)oxovanadium(IV), by electron spin-echo envelope modula-
tion spectroscopy, and observed that the original binary complex was transformed into a
ternary complex with composition VO(pic)(X), where X represents an amino acid; they
reported that its activity was changed substantially by the formation of this ternary com-
plex. So, taking into account the possible application of the metallopicolinate complexes as
insulinomimetic agents, we decided to study formation of ternary complexes in the
nickel(II)–H2dipic–amino acid systems as a contribution to the knowledge of the speciation
of the nickel(II)–H2dipic system in biofluids.
In the stability constants databases [5, 6] there are no reports on the speciation of
nickel(II)–H2dipic with the amino acids aspartic acid (H2asp), glutamic acid (H2glu),
cysteine (H2cys) or histidine (Hhis).

2 Experimental

2.1 Reagents

NiCl26H2O and the amino acids (aspartic acid, glutamic acid, cysteine and histidine all
were from (Merck p.a.). Na2EDTA2H2O and Bromopyrogallol Red indicator from (Merck
p.a.) were used without further purification. The HCl and NaOH solutions were prepared
using 100.0 mmoldm-3 Titrisol Merck ampoules. The NaOH solution was standardized
against potassium hydrogen phthalate (Merck p.a., recrystallized and dried at 120 °C)
using phenolphthalein as indicator, and the HCl solution was standardized with NaOH
solution of known concentration [7]. The solutions were prepared using triply glass-dis-
tilled water, boiled before preparation of the solutions in order to remove dissolved CO2.
To prevent hydrolysis of the NiCl2 stock solution, it contained 100 mmoldm-3 HCl. NiCl2
is hygroscopic and must be weighed as fast as possible. For that reason it is necessary to
standardize the NiCl2 stock solution using a Na2EDTA2H2O solution (0.01 moldm-3) in
a buffered medium (pH 10) using Bromopyrogallol Red as indicator [8]. The acidity of the
NiCl2 stock solution was determined by the Gran method [9]. Potentiometric

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measurements were carried out in aqueous solution using 1.0 moldm-3 NaCl as the ionic
medium. Nitrogen free of O2 and CO2 were used.

2.2 Methods

The potentiometric measurements were done using the following instruments: Thermo
Orion model 520A pH meter, Metrohm EA 876–20 titration vessel, and Lauda Brikmann
RM6 thermostat bath. The sealed 100 mL thermostatted double-walled glass titration
vessel was fitted with a combined Orion Ross 8102BN pH electrode and a titrant inlet,
magnetic stirrer, and an inert nitrogen atmosphere inlet with outlet tubes. The temperature
was maintained at (25.0 ± 0.1) °C by constant circulation of water from the thermostat’s
water bath.
The emf (H) measurements were carried out by means of the REF//S/GE cell, where
REF = Ag/AgCl/3.0 moldm-3 KCl; S = equilibrium solution and GE = glass electrode.
At 25 °C the emf (mV) of this cell follows the Nernst equation, E = E0 ? jh ? 59.16
log10 h, where h represents the free hydrogen ion concentration, E0 is the standard potential
and j is a constant which takes into account the liquid junction potential [10]. The
experiments were carried out as follows: a fixed volume of 0.100 moldm-3 HCl con-
taining NaCl 0.900 moldm-3 NaCl was titrated with successive additions of
0.100 moldm-3 NaOH containing NaCl at ionic strength 1.000 moldm-3 until near
neutrality, in order to determine the parameters E0 and j. Then, aliquots of H2dipic and the
amino acid under study were added and, finally, an aliquot of the nickel(II) stock solution
was added sequentially. The titration was then continued with 0.100 moldm-3 NaOH. The
measurements were done using a total metal concentration MT = 2–3 mmoldm-3 and
molar ratios R = 1, 2 and 4 for the Ni2?–amino acid systems and for the nickel(II):H2
dipic:amino acid system, molar ratios were R = 1:1:1, 1:1:2 and 1:2:1.
The systems Ni2?–amino acids (HiL) were studied according to the reaction scheme:
pH2 O þ qNi2þ þ rHi L
½NiqðOHÞpðHi LÞr þ pHþ ; bpqr

The ternary systems Ni2?–H2dipic–amino acids (HiL) were studied according to the
reaction scheme:
pH2 O þ qNi2þ þ rH2 dipic þ sHi L
½NiqðOHÞpðH2 dipicÞrðHi LÞs þ pHþ ; bpqrs

where HiL represents the amino acids: H2asp, H2glu, H2cys and Hhis, and where
[Niq(OH)p(H2dipic)r(HiL)s] is the ternary (p, q, r, s) complex (the charges are omitted)
and bpqrs is the respective stability constant.
The potentiometric data were analyzed using the program LETAGROP [11, 12] in order
to minimize the function ZB = (h - H)/MT, where ZB is the average number of mole of
H? dissociated per mole of metal, H is the total (analytical) concentration of H?, h rep-
resents the equilibrium concentration of H?, and MT represents the total (analytical)
concentration of nickel(II).
The value of pKw was calculated at the ionic strength of 1.0 moldm-3 NaCl to be 13.69
(± 0.01). Equilibria corresponding to the formation of the hydroxo complexes of nickel(II)
were considered in the calculation of the stability constants of ternary complexes.
The following species were assumed: [Ni(OH)]?, log10 b1,-1 = -9.4(1); Ni(OH)2,
log10 b1,-2 = -16.94(4); and [Ni4(OH)4]4?, log10 b4,-4 = -27.73(3) [13]. For the binary
nickel(II)–H2dipic ststem: Ni(dipic), log10 b = 1.16(7); NiðdipicÞ2 2 , log10 b = 1.4(1)
[13]. The nickel(II)–amino acid binary systems [14] were previously studied by us. Values

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of the stability constants of the nickel(II) hydroxo complexes, the acidity constants of the
ligands, and the stability constants of the binary complexes were kept fixed during the
analysis. The aim was to find a complex or complexes giving the lowest sum of the errors
P
squared, U ¼ ðZBexp  ZBcalc Þ2 , and the fittings were done by testing different (p, q, r) and
(p, q, r, s) combinations.
The species distribution diagrams were done with the computer program HYSS [15],
yielding the bpqr and bpqrs values that are summarized in Tables 2 and 3.

3 Results

3.1 Ionization Constants of the Studied Ligands

The ionization constants in the ionic medium 1.0 moldm-3 NaCl, given in Table 1, are in
good concordance (differences could be 0.1 logarithm unit) with the results obtained
previously by our research group. However the pKa1 of aspartic acid and the pKa2 and pKa3
of cysteine and pKa3 of histidine are different; we really haven’t found an explanation, but
it is important to obtain a lot of data made under the same conditions by different research
groups in order to obtain a more reliable value.

Table 1 Values of log10 bpr and pKi for the ligands studied (25 °C, I = 1.0 moldm-3 NaCl ionic medium)
log10 bpr

Equilibrium H2dipic H2asp H2glu H2cys Hhis

H2 L þ Hþ
H3 Lþ – 1.76(3) 2.32(4) 2.05(3)
H2 L
HL þ Hþ -2.43(2) -3.58(3) -4.15(3) -8.11(3)
H2 L
L2 þ 2Hþ -6.98(2) -13.05(5) -13.52(4) -17.97(4)
HL
L þ Hþ -9.06(7)
HL þ Hþ
H2 Lþ 6.26(5)
þ 2þ 8.76(7)
HL þ 2H
H3 L
Dispersion (r) 0.024 0.031 0.031 0.035 0.035
pKi
pKa1 1.76 2.32 2.05 2.50
2.0b 2.39a 2.04a 1.82b
0.49a 2.24c 2.41c 2.15c 2.50c
pKa2 3.58 4.15 8.11 6.26
2.43 3.7b 4.07a 8.22a 6.08b
2.18a 3.78c 4.22c 8.44c 6.25c
pKa3 9.47 9.37 9.86 9.06
4.55 9.59b 9.50a 10.26a 9.20b
4.62a 9.57c 9.31c 10.62c 8.85c

Values in parentheses are three times the standard deviation [3(log10)] on the last significant figure
a
Reference [6]
b
1.0 moldm-3 NaClO4
c
Reference [16]

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3.2 Nickel(II)–Amino Acid Binary Systems

Figures 1, 2, 3, and 4 show the species distribution diagrams for Ni(II) binary systems with
H2asp, H2glu, H2cys and Hhis, respectively, at the following conditions: MT = 2
mmoldm-3 and molar ratio R = 2. The stability constants of the complexes formed are
summarized in Table 2.

3.3 Ternary Nickel(II) Complexes

3.3.1 Nickel(II)–H2dipic–HiL Systems

Figures 5, 6, 7, and 8 show the species distribution diagrams for Ni(II)–H2dipic ternary
systems with H2asp, H2glu, H2cys and Hhis, respectively, at the following conditions:
MT = 2 mmoldm-3 and molar ratio R = 1:1:1. The stability constants of the complexes
formed are summarized in Table 3.
In the Ni(II)–H2asp system, analysis of the potentiometric data indicates formation of
the complexes [NiHL]?, NiL and [NiL2]2-. The species distribution diagrams are given in
Fig. 1; Ni(II) is abundant at pH \ 2.2, between pH values 2.2–4.2 the acidic complex
[NiHL]? predominates, in the range 4.2 \ pH \ 7 the most important species is NiL,
while at pH [ 7 the complex [NiL2]2- predominates.
In the Ni(II)–H2glu system the analysis indicates formation of the species NiL and
[NiL2]2-. The species distribution diagrams (Fig. 2) show that Ni(II) is abundant at
pH \ 6.5, between the pHs 6.5 and 8 the NiL complex predominates, and at pH [ 8 the
complex [NiL2]2- predominates.
It was observed that in the Ni(II)–H2cys system the complexes [NiHL]?, NiL and
[NiHL2]- form. The species distribution diagrams given in Fig. 3 show that Ni(II) is
abundant at pH \ 6, between pH 4 and 9 the acidic complex [NiHL]? is present in low
quantities as is the species NiL, while at pH [ 6 the most important complex is [NiHL2]-.
In the case of the Ni(II)–Hhis system the complexes [NiH2L]3?, [NiHL]2?, NiL?,
[Ni(HL)2]2?, [NiHL2]? and NiL2 were detected. In Fig. 4 is shown the species distribution
diagrams and we see that Ni(II) is abundant at pH \ 3, between the pHs 1 and 4 the acidic
complex [NiH2L]3? predominates, in the range 4 \ pH \ 6 the most important species is
NiL, the species [NiHL]2?,[Ni(HL)2]2?, [NiHL2]? are formed in low proportions in pH
range 3–7, while the complex NiL2 is very important at pH [ 6.
The potentiometric data analysis for the Ni(II)–H2dipic–H2asp system performed with
the program LETAGROP [11, 12] indicates formation of the mononuclear complexes

Fig. 1 Species distribution 100 Ni2+

diagrams as a function of pH for NiL [Ni(L)2]2-
the Ni(II)–H2asp system in 1.0
75 [Ni(HL)] +
moldm-3 NaCl at 25 °C
% Ni(II)

considering the conditions

50
MT = 2 mmoldm-3 and molar
ratio R = 2
25

0
1 2 3 4 5 6 7 8 9
pH

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Fig. 2 Species distribution 100

Ni2+
diagrams as a function of pH for [Ni(L)2]2-
the Ni(II)–H2glu system in 1.0 75
moldm-3 NaCl at 25 °C NiL

% Ni(II)
considering the conditions 50
MT = 2 mmoldm-3 and molar
ratio R = 2
25

0
3 4 5 6 7 8 9 10
pH

Fig. 3 Species distribution 100

diagrams as a function of pH for 90 Ni2+
[NiH(L)2]-
the Ni(II)–H2cys system in 1.0 80
moldm-3 NaCl at 25 °C 70
% Ni(II)

considering the conditions 60

MT = 2 mmoldm-3 and molar 50
ratio R = 2 40
30
20 NiL
10 [Ni(HL)]+
0
4 5 6 7 8 9 10
pH

Fig. 4 Species distribution 100

Ni2+
diagrams as a function of pH for [Ni(L)2]2-
the Ni(II)–Hhis system in 1.0 75
moldm-3 NaCl at 25 °C NiL
% Ni(II)

considering the conditions

MT = 2 mmoldm-3 and molar 50 [Ni(H2L)]3+
ratio R = 2
[NiH(L)2]+
25
[Ni(HL)]+
0
1 2 3 4 5 6 7 8 9
pH

Ni(dipic)(H2L), [Ni(dipic)(HL)]-, [Ni(dipic)(L)]2- and [Ni(dipic)(L)(OH)]3-. In the spe-

cies distribution diagrams, Fig. 5, we see in the range 2 \ pH \ 3.5 the most important
species is the ternary complex Ni(dipic)(H2L), between 3.5 \ pH \ 6.5 the species
[Ni(dipic)(HL)]- is formed, the species [Ni(dipic)(L)]2- is present between
6.5 \ pH \ 10, and finally the complex [Ni(dipic)(L)(OH)]- is the most important species
at pH [ 10.
In the Ni(II)–H2dipic–H2glu system the complexes Ni(dipic)(H2L), [Ni(dipic)(HL)]-,
[Ni(dipic)(L)]2- and [Ni(dipic)(L)(OH)]3- were detected. The species distribution dia-
grams are shown in Fig. 6. We see that in the range 2 \ pH \ 4 the most important species
is the ternary complex Ni(dipic)(H2L), between 4 \ pH \ 7 the species [Ni(dipic)(HL)]-

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Table 2 Equilibrium constants (log10 bpqr) for the nickel(II)–amino acids systems (25 °C, I = 1.0 moldm-3 NaCl ionic medium)
Equilibrium log10 bpqr

H2asp H2glu H2cys Hhis

Ni2þ þ H2 L
NiHLþ þ Hþ -0.23(4) -3.8 max -3.3-3.61b
a a
Ni2þ þ H2 L
NiL þ 2Hþ -4.83(5)-6.53 -8.37(6)-7.28 -9.4(4)-9.78b
þ -11.9(1)-12.94b
Ni2þ þ 2H2 L
NiHL
2 þ 3H
2þ þ a a
Ni þ 2H2 L
NiL2
2 þ 4H -12.26(8)-14.69 -17.59(1)-16.01 -17.35b
2þ 8.85(6)
Ni þ Hþ þ HL
NiH2 L3þ
2þ 2þ 4.1(2)
Ni þ HL
NiHL
2þ þ þ -0.31(4)-0.84a
Ni þ HL
NiL þ H
2þ 7.6(3)
Ni þ 2HL
NiHL2þ
2
Ni2þ þ 2HL
NiHLþ
2 þ Hþ 2.7(1)
2þ þ
Author's personal copy

Ni þ 2HL
NiL2 þ 2H -2.65(5)-3.0a
Dispersion (r) 0.077 0.072 0.139 0.066
Values in parentheses are three times the standard deviation [3(log10)] on the last significant figure
a
Reference [6]
b
0.2 moldm-3 KCl
J Solution Chem (2015) 44:2144–2153
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Fig. 5 Species distribution 100

- [Ni(dipic)(L)]2-
diagrams as a function of pH for Ni(dipic)(H2L) [Ni(dipic)(HL)]
the Ni(II)–H2dipic–H2asp system 75
in 1.0 moldm-3 NaCl at 25 °C

% Ni(II)
considering the conditions
MT = 2 mmoldm-3 and molar 50
[Ni(dipic)(L)(OH)]3-
ratio R = 1:1:1
25
Ni(dipic)
0
2 3 4 5 6 7 8 9 10 11
pH

Fig. 6 Species distribution 100 [Ni(dipic)(L)]2-

90 [Ni(dipic)(L)(OH)]3-
diagrams as a function of pH for
80 Ni(dipic)(H2L) [Ni(dipic)(HL)] -
the Ni(II)–H2dipic–H2glu system
70
in 1.0 moldm-3 NaCl at 25 °C
% Ni(II)

60
considering the conditions 50
MT = 2 mmoldm-3 and molar 40
ratio R = 1:1:1 30
20 Ni(dipic)
10
0
2 3 4 5 6 7 8 9 10 11
pH

Fig. 7 Species distribution [Ni(dipic)(L)]2-

diagrams as a function of pH for 100
the Ni(II)–H2dipic–H2cys system
in 1.0 moldm-3 NaCl at 25 °C 75
considering the conditions Ni(dipic)(H2L)
% Ni(II)

MT = 2 mmoldm-3 and molar

[Ni(dipic)(HL)]-
ratio R = 1:1:1 50

Ni(dipic)
25
Ni(dipic)22-

0
2 3 4 5 6 7 8 9 10 11
pH

is formed, the complex [Ni(dipic)(L)]2- is present between 7 \ pH \ 10, and finally the
complex [Ni(dipic)(L)(OH)]- is the most important species at pH [ 10.
In the Ni(II)–H2dipic–H2cys system the complexes Ni(dipic)(H2L), [Ni(dipic)(HL)]-
and [Ni(dipic)(L)]2- are observed. The distribution diagrams in Fig. 7, indicate that in the
pH range 2–5.5 the predominant complex is Ni(dipic)(H2L) and the binary complexes
Ni(dipic) and NiðdipicÞ2
2 are formed in low quantities; the species [Ni(dipic)(HL)] is
-

formed in low quantity between pH 5 and 6, and at pH [ 5.5 the ternary complex
[Ni(dipic)(L)]2- predominates. In the Ni(II)–H2dipic–Hhis system the complexes
[Ni(dipic)(L)]- and [Ni(dipic)(L)(OH)]2- are observed. The distribution diagrams are
shown in Fig. 8 and indicate that in the range 2 \ pH \ 10 the binary Ni(II) complexes are

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Fig. 8 Species distribution 100

diagrams as a function of pH for [Ni(dipic)(L)(OH)]2-
the Ni(II)–H2dipic–Hhis system 75
in 1.0 moldm-3 KCl at 25 °C

% Ni(II)
Ni(dipic)
considering the conditions
MT = 2 mmoldm-3 and molar 50 [Ni(dipic)2]2-
ratio R = 1:1:1 [NiH2L]3+ Ni(L)2
[Ni(L)]+
25 +
[NiH(L)2] [Ni(dipic)(L)]-

0
2 3 4 5 6 7 8 9 10 11
pH

Table 3 Equilibrium constants (log10 bpqrs) for the ternary nickel(II)–H2dipc–amino acids systems (25 °C,
I = 1.0 moldm-3 NaCl ionic medium), according to the following reaction
2+ +
scheme: pH2O + qNi + rH2dipic + sHiL [Niq(OH)p(H2dipic)r (HiL)s] + pH , βpqrs

Complexes log10 bpqrs

H2asp H2glu H2cys Hhis

Ni(dipic)H2L 6.04(4) 5.41(6) 4.68(6)

[Ni(dipic)HL]- 2.44(4) 1.20(5) -2.0 max -1.5
[Ni(dipic)L]2- -4.08(6) -5.74(6) -6.80(5) -1.2 max -0.9
[Ni(dipic)L(OH)]3- -14.67(8) -15.78(7) -10.8(2)
Dispersión (r) 0.060 0.064 0.116 0.100
Values in parentheses are three times the standard deviation [3(log10)] on the last significant figure

present, the ternary complex [Ni(dipic)(L)]- is formed at 10 % between the pHs 4 and 11,
and the ternary complex [Ni(dipic)(L)(OH)]2- is abundant at pH [ 10.

4 Conclusions

The analysis of the potentiometric data by means of the computational least-squares program
LETAGROP, taking into account hydrolysis of the nickel(II) cation and the acid/base
reactions of the ligands which were kept fixed during the analysis, indicates that in the
Ni(II)–H2asp system of the complexes [NiHL]?, NiL and [NiL2]2- are formed, while for the
Ni(II)–H2glu system the species NiL and [NiL2]2- are formed. In the Ni(II)–H2cys system
the complexes [NiHL]?, NiL and [NiHL2]- were detected. And, in the case of the Ni(II)–
Hhis system, the complexes [NiH2L]3?, [NiHL]2?, NiL?, [Ni(HL)2]2?, [NiHL2]? and NiL2
are observed. In the nickel(II)–H2dipic–H2asp ternary systems the formation of the com-
plexes Ni(dipic)(H2L), [Ni(dipic)(HL)]-, [Ni(dipic)(L)]2- and [Ni(dipic)(L)(OH)]3- were
observed. In the nickel(II)–H2dipic–H2glu system the species Ni(dipic)(H2L),
[Ni(dipic)(HL)]-, [Ni(dipic)(L)]2- and [Ni(dipic)(L)(OH)]3- were observed. In the nick-
el(II)–H2dipic–H2cys system the complexes Ni(dipic)(H2L), [Ni(dipic)(HL)]- and
[Ni(dipic)(L)]2- were detected. Finally, in the nickel(II)–H2dipic–Hhis system the com-
plexes [Ni(dipic)(L)]- and [Ni(dipic)(L)(OH)]2- were observed.

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J Solution Chem (2015) 44:2144–2153 2153

Acknowledgments The authors thank Dr. Antonio Barriola for valuable discussions. The authors are
grateful for financing provided by the Decanato de Investigación y Desarrollo, from the Simón Bolı́var
University. Lino Hernández and Edgar Del Carpio thanks Simón Bolı́var University for a scholarship.

References
1. Conato, C., Kozłowski, H., Swiatek-Kozłowska, J., Młynarz, P., Remelli, M., Silvestri, S.: Formation
equilibria of nickel complexes with glycyl-histidyl-lysine and two synthetic analogues. J. Inorg. Bio-
chem. 98, 153–160 (2004)
2. Lubes, V.: Vanadium(III) complexes with picolinic acid and dipicolinic acid in aqueous solution.
J. Solution Chem. 34, 899–915 (2005)
3. Yasumatsu, N., Yoshikawa, Y., Adachi, Y., Sakurai, H.: Antidiabetic copper(II)–picolinate: impact of
the first transition metal in the metallopicolinate complexes. Bioorg. Med. Chem. 15, 4917–4922 (2007)
4. Fukui, K., Fujisawa, Y., Ohya-Nishiguchi, H., Kamada, H., Sakurai, H.: In vivo coordination structural
changes of a potent insulin-mimetic agent, bis(picolinato)oxovanadium(IV), studied by electron spin-
echo envelope modulation spectroscopy. J. Inorg. Biochem. 77, 215–224 (1999)
5. Martell, A.E., Smith, M., Motekaitis, R.J.: NIST Critical Stability Constants of metal Complexes
Database. US Department of Commerce, Gaithersburg, MD (1993)
6. Powell, K.J., Pettit, L.D.: IUPAC Stability Constants Database. Academic Software, Otley (1997)
7. Kolthoff, I.M., Stenger, V.A.: Volumetric Analysis, vol. II, p. 94. Interscience Publishers, New York
(1947)
8. Jeffery, G.H., Bassett, J., Mendham, J., Denney, R.C.: Vogel’s Textbook of Quantitative Chemical
Analysis, 5th edn, p. 327. Longman Scientific and Technical, UK (1989)
9. Gran, G.: Determination of the equivalence point in potentiometric titrations. Part II. Anal. 77, 661–671
(1952)
10. Biedermann, G., Sillén, L.G.: The hydrolysis of metal ions. IV. Liquid-junction potentials and con-
stancy of activity factors in NaClO4–HClO4 ionic medium. Ark. Kemi 5, 425–440 (1953)
11. Brito, F., Araujo, M.L., Lubes, V., D’Ascoli, A., Mederos, A., Gili, P., Domı́nguez, S., Chinea, E.,
Hernández-Molina, R., Armas, M.T., Baran, E.J.: Emf(H) data analysis of weak metallic complexes
using reduced formation functions. J. Coord. Chem. 58, 501–512 (2005)
12. Sillén, L.G., Warnqvist, B.: High-speed computers as a supplement to graphical methods. VI. A strategy
for two-level Letagrop adjustment of common and ‘‘group’’ parameters. Features that avoid divergence.
Ark. Kemi 31, 315–339 (1969)
13. Veliz, L., Martı́nez, J.D., Araujo, M.L., Brito, F., Lubes, G., Rodrı́guez, M., Lubes, V.: Estudio de la
hidrólisis del ion Niquel(II) y de la formación de los complejos de Niquel(II) con los ácidos Picolı́nico y
Dipicolı́nico en NaCl 1,0 moldm–3 a 25°C. Avances Quı́m. 6, 38 (2011)
14. Lema J. Estudio de formación de los complejos de nı́quel(II) con lo aminoácidos: ácido aspártico, ácido
glutámico, histidina y cisteı́na mediante medidas de emf(H) en NaCl 1,0 M a 25 °C. Undergraduate
thesis, Escuela de Quı́mica, Facultad de Ciencias, Universidad Central de Venezuela (2010)
15. Lderighi, L., Gans, P., Ienco, A., Peters, D., Sabatini, A., Vacca, A.: Hyperquad simulation and spe-
ciation (HySS): a utility program for the investigation of equilibria involving soluble and partially
soluble species. Coord. Chem. Rev. 184, 311–318 (1999)
16. Centeno, M.M., Martı́nez, J.D., Araujo, M.L., Brito, F., Carpio, E., Hernández, L., Lubes, V.R.:
Solution equilibria of ternary systems involving nickel(II) ion, picolinic acid, and the amino acids
histidine, cysteine, aspartic and glutamic acids. J. Solution Chem. 43, 1011–1018 (2014)

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