Journal of Solution Chemistry, Vol. 34, No.

8, August 2005 (

C 2005)

DOI: 10.1007/s10953-005-6253-8

Vanadium(III) Complexes with Picolinic Acid

and Dipicolinic Acid in Aqueous Solution
Vito Lubes1

Received December 9, 2004; Revised March 9, 2005

The complex species formed in aqueous solution (25 ◦ C, I = 3.0 mol-dm−3 KCl ionic
medium) between V3+ cation and the ligands: picolinic acid (Hpic, HL) and dipicolinic
acid (H2 dipic, H2 L), have been studied potentiometrically and by spectrophotometric
measurements. The application of the least-squares computer program LETAGROP
to the experimental emf (H) data, taking into account the hydrolytic species of V3+
ion, indicates that under the employed experimental conditions, the formation of the
complexes [VL]2+ , [V(OH)L]+ , [VL2 ]+ , [VL3 ], [V2 OL4 ] with picolinic acid and the
complexes [VL]+ , [V(OH)L], [V(OH)2 L]− , [V(HL)(L)], and [VL2 ]− with dipicolinic
acid were observed. The stability constants of the complexes formed were determined
by potentiometric measurements, and spectrophotometric measurements were done in
order to perform a qualitative characterization of the complexes formed in aqueous
solution.

KEY WORDS: Vanadium(III) complexes; solution equilibria; potentiometric studies;

stability constants; speciation.

1. INTRODUCTION
Pyridinecarboxylic acids and their derivatives are present in many natural
products. They are of special interest to medicinal chemists, because of the wide
variety of physiological properties displayed by the natural and many synthetic
derivatives.(1) They are also important from the industrial point of view; for ex-
ample, in nuclear reactor decontamination, where the LOMI (low oxidation state
metal ion) decontamination process uses V(II)/V(III) picolinic acid complexes in
the decontamination solutions.(2,3)
2-Pyridinecarboxylic acid, also known as picolinic acid (Hpic), contains a
carboxylic group in the ortho-position to the nitrogen in the pyridine ring, acting
as a bidentate ligand by (N, COO− ) coordination. It is formed in the body (Hpic)

1 Departamento de Quı́mica, Universidad Simón Bolı́var (USB), Apartado 89.000, Caracas 1080 A,
Venezuela; e-mail: lubesv@usb.ve.

899
0095-9782/05/0800-0899/0

C 2005 Springer Science+Business Media, Inc.
900 Lubes

as an intermediate in the triptophan degradation pathway and it is also an approved

food supplement. In addition, Chromax, is the trade mark name of the Cr(pic)3
complex, which is currently being used as a food additive and has been shown
to assist diabetic patients in maintaining glycemic control.(4,5) The pyridine-2,6-
dicarboxylic acid, also known as dipicolinic acid (H2 dipic), is a versatile N ---- O
donor capable of forming stable chelates(6) 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.(7)
The V(III)-picolinic acid system has been studied before by potentiometric
titrations(8) and the formation of an unique V(pic)3 complex in aqueous solution
was reported. More recently, Chatterjee et al.(9) realized the synthesis and struc-
tural determination of the [V(pic)3 ]·H2 O complex, reporting unexpected highly
stable properties shown by this vanadium(III) complex, especially towards oxi-
dation. The bidentate chelating ligand is coordinated through the pyridine ring
nitrogen and the carboxylate oxygen to the vanadium(III) cation, generating a
highly distorted octahedral geometry.
Chatterjee et al.(7) studied the formation of highly stable vanadium(III) com-
plexes involving dipicolinic acid. They reported homo- and heterochelates involv-
ing H2 dipic and some other bidentate chelating ligands, and the synthesis and
characterization of [V(dipic)(Hdipic)(H2 O)]·3H2 O. They also obtained the struc-
ture by X-ray crystallography of the seven-coordinated mononuclear V(III) com-
plex, [V(dipic)(pic)(H2 O)2 ]·H2 O, which contains two different α-N-heterocyclic
carboxylates and has a pentagonal bipyramidal structure with dipicolinate and
picolinate ligands occupying the pentagonal equatorial plane and two-coordinated
water molecules in the two axial sites.
The vanadium(III) maltolato (ma) complex, V(ma)3 , showed a similar activ-
ity to normalize the glucose level in the STZ-diabetic rat to the benchmark com-
pound, bis(maltolato)oxovanadium(IV), which is an established insulin-enhancing
agent.(10) Taking into account the results obtained with the V(III)-maltolate com-
plexes, Thompson and Orvig(11) considered that the vanadium(III) picolinate com-
plex might also have some insulinomimetic activity. However, this complex has
not been tested for biological activity, but is expect to have some activity, consid-
ering the modest glucose-lowering activity showed by the analogue of V(IV), the
VO(pic)2 complex.(12)
Though there was a previous report of a vanadium(III) complexes with pi-
colinic acid,(8) we decided to re-examine the speciation of this system, because
in that work(8) only the formation of one complex, V(pic)3 , was considered and
it was expected that the speciation of this system might contain more complexes
that were not taken into account. The speciation of the vanadium(III) dipicolinic
acid system had not been studied before.(13) For that reason it is interesting to
study this system in order to compare the results with the V(III)-picolinic acid
system.
Vanadium(III) Complexes with Picolinic Acid and Dipicolinic Acid in Aqueous Solution 901

In this work we report the speciation of the V(III)-picolinic acid and V(III)-
dipicolinic acid systems. Potentiometry was used to determine the stoichiometries
and stability constants of the complexes formed, and UV–vis measurements were
carried out to understand qualitatively the structure of the complexes formed in
aqueous solution.

2. EXPERIMENTAL
2.1. Reagents
The VCl3 (Merck p.a) and the pyridinecarboxylic acids, picolinic acid (Hpic)
and dipicolinic acid (H2 dipic) (Merck 98%) were used without purification. The
HCl and KOH solutions were prepared using 100.0 mM (mM = mmol-dm−3 )
Titrisol Merck ampoules. The KOH solution was standardized against potassium
hydrogen phthalate. The solutions were prepared using triple glass-distilled water
that has been boiled before the preparation of the solutions in order to remove
dissolved CO2 . To prevent the hydrolysis of the VCl3 stock solution, it contained
200 mM HCl and was maintained under a H2 atmosphere in the presence of a Pt-
platinized net in order to avoid oxidation of the V(III) solution to V(IV).(14,15) In
this case, the H2 can not induce reduction to V(II), because the V(III)/V(II) standard
potential is negative (E 0 = −0.26 V).(3) Moreover, if there is any oxidation to
V(IV), the solution is immediately reduced to V(III) because the standard potential
of the reaction,
1
VO2+ + H+ + H2 (g)
V3+ + H2 O(l)
2
is 366.3(3) mV.(16) Under these conditions, the V(III) solution can be maintained.
The stability of the V(III) solution was checked periodically by spectrophotometric
measurements and it was shown to be stable for weeks.
The emf (H) measurements were carried out in aqueous solution at an ionic
strength of 3.0 mol-dm−3 in KCl. Nitrogen free O2 and CO2 was used to maintain
the inert atmosphere.

2.2. Methods
The emf (H) measurements were done using the following instruments: a
Thermo Orion model 420A+ pH meter, a Metrohm EA 876–20 titration vessel,
a Lauda Brikmann RM6 thermostat bath, a Shimadzu UV-1601 PC spectropho-
tometer, and a quartz cell with a 10.0 mm path length. The sealed 100 mL ther-
mostatted double-walled glass titration vessel was fitted with a combined Orion
Ross 8102 BN pH electrode and titrant inlet, magnetic stirrer, and inert nitrogen
atmosphere inlet and outlet tubes. The temperature was maintained at 25.0(1) ◦ C
by constant circulation of water from the thermostat bath.
902 Lubes

The emf (H) measurements were carried out by means of the REF//S/GE cell,
where REF = Ag, AgCl/3.0 M KCl; S = equilibrium solution and GE = glass
electrode. At 25 ◦ C the emf (mV) of this cell follows the Nernst equation, E =
E 0 + j h + 59.16 log 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.(17)
The experiments were carried out as follows:(18) a fixed volume of 0.100 mol-
dm HCl was titrated with successive additions of 0.100 mol-dm−3 KOH until
−3

near neutrality in order to get the parameters E0 and j. Then, known weights of the
ligands and an aliquot of V(III) stock solution were added sequentially. Finally,
the titration was continued with 0.100 mol-dm−3 KOH. The measurements were
done using a total metal concentration, B = 2–3 mM and ligand/metal ratios of
R = 1/1, 2/1, 4/1 and 10/1 with the V(III)-picolinic acid system and using the
ligand/metal ratios, R = 1/1 and 2/1 with the V(III)-dipicolinic acid system.
First, the ionization constants of the ligands, Hpic and H2 dipic, were deter-
mined (LETAGROP software, Table I). Figure 1 shows the formation function,
Z(pH), of the dipicolinic acid system, where Z represents the average number of
H+ dissociated per mole of dipicolinic acid (H2 dipic), according to the reaction,
H2 L
H2− p L + pH+ . At pH < 2, the function has a value of zero, which indicates

Table I. Values of β pr and pKi for the H+ -Hpic and H+ -H2 dipic Systems
(25 ◦ C, I = 3.0 mol-dm−3 KCl ionic medium)

log β pr
Equilibrium H+ -pic H+ -dipic

HL + H+
H2 L+ 1.26(5) —
HL
L− + H+ −5.62(2) —
H2 L
HL− + H+ — −2.57(2)
H2 L
L2− + 2H+ — −7.25(3)
Dispersion σ (z) 0.015 0.019
No. of data points 64 64
No. of titrations 2 2
Concentration of ligand (mmol-dm−3 ) 2.3–2.9 2.3–2.8
pH range 1.8–9.5 1.8–5.6
pKi
H2 L+ -HL 1.26(5) —
HL-L− 5.62(2) —
H3 L3+ -H2 L — 0.49a
H2 L-HL− — 2.57(2)
HL− -L2− — 4.68(4)

Note. Values in parentheses are the standard deviations [3σ (log β)] in the last
significant figure.
a Ref. 22 (1.0 mol-dm−3 NaClO , 25 ◦ C).
4
Vanadium(III) Complexes with Picolinic Acid and Dipicolinic Acid in Aqueous Solution 903

Fig. 1. Z(pH), average number of H+ dissociated per mole of dipicolinic

acid, according to the reaction H2 L
H2− p L− p + pH+ , in KCl 3.0 mol-
dm−3 ionic medium at 25 ◦ C. The continuous curve was drawn using the
stability constants of Table I.

that the most important species is the protonated ligand, H2 L, at pH ∼ 3.5, z has
a value of 1, which corresponds to the formation of the HL− species and finally at
pH > 5.5 z tends to 2, which corresponds to the predominance of the deprotonated
ligand, L2− . The values of pKi obtained in a 3.0 mol-dm−3 KCl ionic medium are
also presented in Table I.
The system V3+ /picolinic acid was studied according to the reaction scheme:
pH2 O + qV3+ + r HL
[(OH) p (V)q (HL)r ]3q− p + pH+ β pqr
and the V3+ /dipicolinic acid complexes were studied according to the reaction
scheme:
pH2 O + qV3+ + r H2 L
[(OH) p (V)q (H2 L)r ]3q− p + pH+ β pqr

The potentiometric data were analyzed using the program LETAGROP,(19,20)

in order to minimize the function z B = (h − H )/B, where H is the total (analytical)
concentration of H+ , h represents the equilibrium concentration of H+ , and B
represents the total (analytical) concentration of V3+ .
Equilibria corresponding to the formation of the hydroxo complexes of V(III)
were considered in the calculation of the stability constants of the complexes.
The following species were assumed: [V(OH)]2+ , logβ1,−1 = −3.07(3); [V2 O]4+ ,
log β2,−2 = −3.94(2); and [V2 O(OH)]3+ , log β2,−3 = −7.87(9).(16) The stabil-
ity constant of the hydroxo complexes of V(III) and the stability constants of
the ligands were kept fixed during the analysis. The aim of the analysis was
to find

a complex or complexes giving the lowest sum of the errors squared,
exp
U = (z B − z calc 2
B ) , by testing different (p, q, r) combinations.
The species distribution diagrams were done with the computer program
HYSS,(21) yielding the β pqr values summarized in Tables IV and VI.
904 Lubes

2.3. Spectrophotometric Measurements

The spectrophotometric measurements were performed in order to get infor-
mation on the complexes formed in aqueous solution. The spectra were measured
using the total metal concentration, B = 0.003 mol-dm−3 and the ratio, R = 2, at
different pH values in both systems.

3. RESULTS AND DISCUSSION

3.1. Ionization Constants of Picolinic and Dipicolinic Acids
The ionization constants (Table I) in the ionic medium 3.0 mol-dm−3 KCl
are in both cases in good agreement with the literature values, considering the
differences in ionic strength and ionic medium.(13,22,23) For picolinic acid, the pK1
corresponds to the deprotonation of the carboxylic group in the species H2 L+ and
the pK2 corresponds to the deprotonation of the pyridine in the HL species, because
this pKa value is in close agreement with that for pyridine pK a ( pK a = 5.24).(13)
This permits us to say that the HL species corresponds to the zwitterionic form
of the ligand. For dipicolinic acid, only the acid-base behavior was measured
in the range 1.8 < pH < 5.5, and in this range were only detected two pKa s.
The first deprotonation (H3 L+ /H2 L) has a pK a = 0.49,(22) but it was impossible
to measure it with a glass electrode because of the large contribution of the
liquid union potential. The H2 L species should correspond to the zwitterionic
form of dipicolinic acid. The pKa of the equilibrium H2 L/HL− corresponds to
the deprotonation of the second carboxylic group and the equilibrium HL− /L2−
corresponds to the deprotonation of the pyridine group (pyridine pK a = 5.24).(13)

3.2. Stability Constants of the Complexes Formed

3.2.1. V(III) Picolinic Acid System
In Table II are presented the potentiometric, V(mL) and E(mV), data for the
V(III)-picolinic acid system.
In this case the complexes were studied in the range, 1.5 < pH < 7, we
could not study the reaction of complex formation at higher pH, because of the
instability of the potential reading at pH > 7. Therefore, only the data collected
below this pH were used to calculate the complex model (p, q, r) and the cor-
responding stability constants, β p,q,r . The potentiometric emf (H) data analysis
was performed with LETAGROP(19,20) Table III is shown as an example of the
equilibrium analysis performed in the V(III)-picolinic acid system. In this table
it is observed that the model, which presents the best fit of the experimental
data, is made up of the mononuclear complexes, [VL]2+ , [V(OH)L]+ , [VL2 ]+
and [VL3 ], and the µ-oxodivanadium(III) complex [V2 OL4 ]. The good agreement
between the experimental data (dotted curve) and the model (continuous line)
Vanadium(III) Complexes with Picolinic Acid and Dipicolinic Acid in Aqueous Solution 905

Table II. Potentiometric V(mL), E(mV) Data for the V(III)-Picolinic Acid System at I =
3.0 mol-dm−3 of KCl and 25 ◦ C
V (mL) E (mV) V (mL) E (mV) V (mL) E (mV) V (mL) E (mV) V (mL) E (mV) V (mL) E (mV) V (mL) E (mV)

Hs = 0.0290; Bs = 0.0034; Cs = 0.0034; Ht = −0.0997; Vo = 36.49, E0 = 433.6, j = −6.6

0.0 342.4 5.0 324.8 9.5 294.4 11.4 263.3 12.4 225.9
0.5 341.0 6.0 319.9 10.0 288.3 11.6 259.2 12.5 219.4
1.0 339.4 7.0 314.5 10.5 281.5 11.8 253.0 12.6 211.3
2.0 336.1 8.0 308.0 10.8 276.2 12.0 245.8 12.7 203.1
3.0 332.6 8.5 304.0 11.0 272.6 12.2 236.5
4.0 328.8 9.0 299.7 11.2 269.0 12.3 233.9

Hs = 0.0275; Bs = 0.0032; Cs = 0.0065; Ht = −0.0997; Vo = 38.48, E0 = 432.7, j = 0.5

0.0 341.3 6.0 320.3 10.5 288.4 12.0 264.6 12.7 244.4 13.3 217.8 13.9 154.0
1.0 338.5 7.0 315.4 11.0 281.8 12.2 258.9 12.8 240.9 13.4 212.0 14.0 122.6
2.0 335.6 8.0 309.5 11.2 278.7 12.3 256.2 12.9 236.3 13.5 205.0
3.0 332.1 9.0 302.6 11.4 275.2 12.4 253.4 13.0 234.2 13.6 196.5
4.0 328.6 9.5 298.5 11.6 272.3 12.5 250.6 13.1 228.1 13.7 187.9
5.0 324.6 10.0 293.8 11.8 267.6 12.6 247.6 13.2 223.3 13.8 174.0

Hs = 0.0249; Bs = 0.0029; Cs = 0.0117; Ht = −0.0997; Vo = 42.47, E0 = 432.8, j = −2.6

0.0 338.4 9.0 303.1 12.0 272.1 13.5 228.0 14.4 139.4 15.3 94.3 16.2 54.4
1.0 335.8 9.5 299.5 12.2 267.7 13.6 223.1 14.5 132.8 15.4 91.2 16.3 48.0
2.0 332.8 10.0 295.4 12.4 263.2 13.7 213.1 14.6 126.6 15.5 87.0 16.4 40.4
3.0 329.8 10.5 290.8 12.6 259.3 13.8 206.1 14.7 121.1 15.6 82.8 16.5 31.6
4.0 326.4 11.0 285.6 12.8 254.1 13.9 197.0 14.8 115.9 15.7 77.3 16.6 22.3
5.0 323.0 11.2 283.2 13.0 248.9 14.0 184.7 14.9 111.2 15.8 73.5 16.7 12.4
6.0 318.7 11.4 280.7 13.2 240.8 14.1 170.9 15.0 109.0 15.9 68.6 16.8 1.6
7.0 314.4 11.6 277.8 13.3 236.7 14.2 158.2 15.1 104.8 16.0 65.9
8.0 309.1 11.8 274.6 13.4 232.4 14.3 147.8 15.2 100.4 16.1 60.6

Hs = 0.0195; Bs = 0.0023; Cs = 0.0229; Ht = −0.0997; Vo = 54.48, E0 = 433.0, j = −0.2

0.0 330.5 9.5 294.1 13.3 240.2 14.3 182.7 15.6 140.5 18.2 105.6 22.3 55.9
1.0 328.1 10.0 290.6 13.4 236.3 14.4 177.1 15.8 136.6 18.5 102.3 22.6 50.3
2.0 325.4 10.5 286.5 13.5 232.4 14.5 172.2 16.0 134.1 18.9 98.2 23.0 41.7
3.0 322.5 11.0 281.7 13.6 227.5 14.6 167.8 16.2 130.1 19.3 93.6 23.3 33.1
4.0 319.5 11.4 277.2 13.7 222.4 14.7 162.5 16.4 127.0 19.7 89.3 23.5 26.6
5.0 316.0 11.8 272.6 13.8 216.2 14.8 160.7 16.7 123.2 20.1 85.3 23.7 18.7
6.0 312.4 12.2 266.6 13.9 209.2 14.9 156.4 17.0 119.5 20.5 80.7 23.9 8.7
7.0 308.2 12.6 259.4 14.0 201.8 15.0 153.7 17.3 115.8 21.0 74.8
8.0 303.3 13.0 250.6 14.1 194.9 15.2 148.8 17.6 112.3 21.5 67.7
9.0 297.3 13.2 243.7 14.2 187.9 15.4 144.6 17.9 108.6 22.0 60.7

Note. Hs , Bs , Cs = initial concentration of H+ , V3+ and ligand (mol-dm−3 ); Ht = titrant concentration

(mol-dm−3 ) (KOH concentration), Vo = initial volume of titration, E0 = standard potential and j =
liquid junction potential.

can be observed in Fig. 2. The respective stability constants are summarized in

Table IV.
In the Fig. 3 the distribution of V3+ species is shown as a function of pH for the
V -picolinic acid system at the following conditions: (a) B = 0.003 mol-dm−3
3+

and the ratio R = 2; and (b) B = 0.003 mol-dm−3 and the ratio R = 10.

3.2.2. V(III) Dipicolinic Acid System

In Table V are presented the potentiometric V(mL) and E(mV) data for the
V(III)-dipicolinic acid system.
 906

Table III. Log β p, q, r for Different (p, q, r) Combinations Versus σ (zB ) for the V(III)-Picolinic Acid System, Considering the Reaction
Scheme: pH2 O + qV3+ + r HL
Vq (OH) p (HL)r + pH+

Log β p ,q,r

VL2+ VL+
2 VL3 V(OH)L+ VHL3+ V2 OL3+ V2 OL2+
2 V2 OL4 V(OH)L−
3 σ (zB )

1.23(6) 1.02(5) 0 −2.7(1) 3.45(4) 0 0.093

0.44(5) −0.04(2) 0 0.083
1.14(5) 0.76(4) 0 −3.4(1) 3.36(4) −2.3(3) 0.082
0.26(6) −0.08(4) −4.2(1) 2.34(6) 0.078
0.68(5) 0.31(4) 0 −3.9(1) 2.78(5) 0.074
0.49(6) 0.72(4) −0.10(3) −2.8(1) 1.7(2) −6.84(6) 0.071
0.56(8) 1.12(4) 0.41(3) −5.55(5) 0.070
0.11(5) −0.26(3) −4.3(1) 0.068
0.62(5) 1.44(2) 0.42(3) −2.21(7) 2.08(7) −1.26(4) 0.039
−0.2(3) 1.68(2) 0.65(3) −0.61(4) 0.039
0.38(9) 1.68(2) 0.68(3) −2.15(7) 0 −0.57(4) 0.036
0.39(9) 1.68(2) 0.68(3) −2.12(7) −0.55(4) 0.035
Lubes
Vanadium(III) Complexes with Picolinic Acid and Dipicolinic Acid in Aqueous Solution 907

Fig. 2. ZB (pH), average number of H+ dissociated per mole of vanadium(III)

for the V(III)-picolinic acid system (Hpic, HL), according to the reaction:
pH2 O + qV3+ + r HL
[(OH) p (V)q (HL)r ]3q− p + pH+ , in 3.0 mol-dm−3 KCl
ionic medium at 25 ◦ C and the following B and R ranges: 0.002 mol-dm−3 < B
< 0.003 mol-dm−3 and 1 < R < 10. The continuous curve was drawn using the
stability constants of Table IV.

For the vanadium(III) dipicolinic acid system, the model that best fitted the
experimental potentiometric data included only mononuclear vanadium(III) com-
plexes: [VL]+ , [V(OH)L], [V(OH)2 L]− , [V(HL)(L)] and [VL2 ]− . The calculated
zB versus log h curves (continuous line) in Fig. 4 indicate the correctness of
the model for this system. The respective stability constants are summarized in
Table VI.
In Fig. 5 the distribution diagram of the V3+ -dipicolinic acid system is
shown considering the total metal concentration B = 0.003 mol-dm−3 in both
cases where (a) R = 1 and (b) R = 2.

Table IV. Equilibrium Constants for the V(III)-Picolinic

Acid System ( 25 ◦ C, I = 3.0 mol-dm−3 KCl Ionic Medium)

Equilibrium Log β pqr

V3+ + HL   VL2+ + H+ 0.39(9)

H2 O + V3+ + HL   V(OH)L+ + 2H+ −2.12(7)
+
V3+ + 2HL   VL2 + 2H+ 1.68(2)
V3+ + 3HL   VL3 + 3H
+ 0.68(3)
H2 O + 2V3+ + 4HL   V2 OL4 + 6H+ −0.55(4)
Dispersion σ (zB ) 0.035
No. of data points 391
No. of titrations 8
Concentration of ligand (mmol-dm−3 ) 3.43–22.91
Concentration of V(III) (mmol-dm−3 ) 2.29–3.43
pH range 1.7–7.2

Note. Values in parentheses are standard deviations [3σ (log

β)] on the last significant figure.
908 Lubes

Fig. 3. Species distribution diagram as a function of pH for the V(III)-

picolinic acid (HL) system for the conditions (a) B = 0.003 mol-dm−3 and
ligand–metal R = 2 and (b) B = 0.003 mol-dm−3 and ligand–metal R =
10, in 3.0 mol-dm−3 KCl ionic medium at 25 ◦ C. Calculated considering
the β pqr values of Table IV.

3.3. Spectrophotometric Results

The electronic absorption spectra for these systems were measured in order
to get qualitative information of the complexes formed in aqueous solution at
different pH values. In Fig. 6 the spectra of the V3+ -picolinic acid system are
presented for the conditions, B = 0.003 mol-dm−3 , R = 2. The insert spectrum
shows absorption bands in the pH range where the complexes [VL]2+ , [V(OH)L]+
and [VL2 ]+ are predominant and these bands are characteristic of electronic d ---- d
transitions with extinction coefficients ε < 50 M−1 -cm−1 , typical of the d ---- d elec-
tronic transition in the visible region for vanadium(III) complexes.(24) However,
what is important is the fact that at higher pH (pH > 3), the formation of the
µ-oxodivanadium(III) complex [V2 OL4 ] begins, see Fig. 3a. When the formation
of this complex starts, the solution turns a brown color, very characteristic of
the µ-oxo V(III) complexes.(25) The [V2 OL4 ] complex shows two LMCT bands
typical of V ---- O ---- V moiety(25) with λmax = 501 nm, ε = 2122 M−1 -cm−1 and
λmax = 627 nm, ε = 930 M−1 -cm−1 . These spectral bands confirm the formation
of the [V2 OL4 ] complex detected by the potentiometric emf (H) measurements,
and the UV–vis spectra have the same characteristics (λmax and ε) as the spectra
reported for dimeric µ-oxo V(III) complexes with similar compositions.(25−27)
 Table V. Potentiometric V (mL), E (mV) Data for the V(III)-Dipicolinic Acid System at I = 3.0 mol-dm−3 of KCl and 25 ◦ C

V (mL) E (mV) V (mL) E (mV) V (mL) E (mV) V (mL) E (mV) V (mL) E (mV) V (mL) E (mV)

Hs = 0.0308; Bs = 0.0036; Cs = 0.0036; Ht = −0.0997; Vo = 34.51, E0 = 432.2; j = −12

0.0 348.1 6.0 327.5 10.5 297.6 12.2 265.3 12.9 222.0 13.5 165.0
1.0 345.1 7.0 322.8 11.0 291.0 12.4 258.7 13.0 216.4 13.6 157.1
2.0 342.1 8.0 317.5 11.3 286.9 12.5 254.7 13.1 200.5 13.7 147.9
3.0 338.7 9.0 310.5 11.5 283.4 12.6 247.0 13.2 189.6 13.8 139.1
4.0 335.4 9.5 306.8 11.8 277.5 12.7 239.9 13.3 182.0 13.9 129.6
5.0 331.5 10.0 302.4 12.0 272.7 12.8 232.0 13.4 173.7 14.0 119.2
Hs = 0.0308; Bs = 0.0036; Cs = 0.0073; Ht = −0.0997; Vo = 34.51; E0 = 433.5; j = −1.8
0.0 348.9 10.0 309.8 13.2 277.5 14.8 231.1 15.6 125.6 16.4 36.0
1.0 346.2 10.5 306.3 13.5 272.3 14.9 222.8 15.7 105.5 16.5 31.4
3.0 340.3 11.0 302.4 13.7 267.5 15.0 214.8 15.8 89.2 16.6 27.5
5.0 333.6 11.5 298.1 14.0 261.8 15.1 210.5 15.9 76.6 16.7 23.5
6.0 329.9 12.0 292.9 14.2 256.3 15.2 200.0 16.0 65.3 16.8 19.3
7.0 325.8 12.5 287.5 14.4 250.1 15.3 186.9 16.1 55.6 16.9 16.5
8.0 321.1 12.8 283.5 14.6 241.5 15.4 171.8 16.2 47.7 17.0 13.1
9.0 316.0 13.0 280.7 14.7 236.7 15.5 144.1 16.3 41.5 17.1 10.3

Note. Hs , Bs , Cs = initial concentration of H+ , V3+ and ligand (mol-dm−3 ); Ht = titrant concentration (mol-dm−3 ) (KOH concentration),
Vo = initial volume of titration, E0 = standard potential and j = liquid junction potential.
Vanadium(III) Complexes with Picolinic Acid and Dipicolinic Acid in Aqueous Solution
909
910 Lubes

Fig. 4. ZB (pH), average number of H+ dissociated per mol of vanadium(III)

for the V(III)-dipicolinic acid system (H2 dipic, H2 L), according to the reaction:
pH2 O + qV3+ + r H2 L
[(OH) p (V)q (H2 L)r ]3q− p + pH+ , in 3.0 mol-dm−3
KCl ionic medium at 25 ◦ C and the following B and R ranges: 0.002 mol-dm−3
< B < 0.003 mol-dm−3 and 1 < R < 2. The continuous curve was drawn using
the stability constants of Table VI.

The electronic absorption spectra for the V3+ -dipicolinic acid system were
recorded at different pHs for the conditions B = 3 mM and R = 2 (Fig. 7), only
one band is observed in the 400 nm region that increases when the pH is in-
cremented. This band is the characteristic charge-transfer band of the vanadium
hydroxide complex.(25) Another important observation, which we can glean from
the absorption spectra, is the absence of a dimeric µ-oxovanadium(III) complex in
this system. It permits us to confirm the formation of monomeric complexes of the
V(III)-dipicolinic acid system obtained by potentiometric emf (H) measurements.

Table VI. Equilibrium Constants for the V(III)-Dipicolinic Acid

System (25 ◦ C, I = 3.0 mol-dm−3 KCl Ionic Medium)

Equilibrium Log β pqr

V3+ + H2 L
VL+ + 2H+ 1.16(2)

H2 O + V3+ + H2 L
V(OH)L + 3H+ −3.38(3)
2H2 O + V3+ + H2 L
V(OH)2 L− + 4H+ −10.36(2)
V3+ + 2H2 L
V(HL)(L) + 3H+ 1.85(3)
V3+ + 2H2 L
VL− 2 + 4H
+ −0.96(2)
Dispersion σ (zB ) 0.023
No. of data points 257
No. of titrations 6
Concentration of ligand (mmol-dm−3 ) 3.57–7.25
Concentration of V(III) (mmol-dm−3 ) 2.4–3.61
pH range 1.4–7.1

Note. Values in parentheses are standard deviations [3σ (log β)] on the last
significant figure.
Vanadium(III) Complexes with Picolinic Acid and Dipicolinic Acid in Aqueous Solution 911

Fig. 5. Species distribution diagram as a function of pH for the V(III)-

dipicolinic acid (H2 L) system for the conditions (a) B = 0.003 mol-
dm−3 and ligand–metal R = 1 and (b) B = 0.003 mol-dm−3 and
ligand–metal R = 2, in 3.0 mol-dm−3 KCl ionic medium at 25 ◦ C.
Calculated considering the β pqr values of Table VI.

Fig. 6. Electronic absorption spectra for the V(III)-picolinic acid (HL) system
(B = 0.003 mol-dm−3 , R = 2) at the pH values: 1.6, 2.1, 2.3 , 3.1, and 3.8. The
inset shows the d ---- d transition region attributed to the complexes [VL]2+ , [VL
(OH)]+ and [VL2 ]+ .
912 Lubes

Fig. 7. Electronic absorption spectra for the V(III)-dipicolinic acid (H2 L) system
(B = 0.003 mol-dm−3 , R = 2) at the pH values: 1.7, 2.8, 3.2, 4.8, and 6.7.

4. DISCUSSION
The aim of this paper was to determine the speciation of the complexes formed
between the vanadium(III) ion and the pyridinecarboxylic acids: picolinic and
dipicolinic acids. Table IV shows the β pqr values for the vanadium(III) picolinic
acid system. In this case, we observed the formation of mononuclear complexes
[VL]2+ , [V(OH)L]+ , [VL2 ]+ and [VL3 ], and the binuclear [V2 OL4 ] complex.
In all the cases, the order of magnitude of the constants obtained indicate that
picolinic acid act as a bidentate ligand coordinated to the vanadium(III) ion by the
pyridine nitrogen and the oxygen of the carboxylic group. The pKa value of the
hydrolysis of the VL2+ complex is 2.5:
H2 O + VL2+  V(OH)L+ + H+ pK a = 2.5 ± 0.1
corresponding to the hydrolysis of one water molecule coordinated to the VL2+
complex and comparable to the first pKa of the vanadium(III) ion (logβ = −3.07 ±
0.05).(16)
The logarithm of the “stepwise” formation constant of the µ-oxovanadium(III)
complex is 25.86, which indicates that the four picolinates are acting as bidentate
ligands.
V2 O4+ + 4L−  V2 OL4 log β = 25.86 ± 0.05
The species distribution diagram of this system for the experimental condition
B = 3 mM and R = 2 (Fig. 3a) indicates that the complex [VL]2+ is formed to
a lesser extent with a 20% maximum at pH 1.8. The complex [VL2 ]+ is formed
with a 70% maximum at pH 2.5 and [V2 OL4 ] is the most abundant complex at
pH > 4. In Fig. 3b is presented the species distribution diagram for the conditions
B = 3 mM and R = 10; in this case, the [VL2 ]+ complex is abundant at pH = 1.8,
the complex [VL3 ] is important in the pH range 2.7 < pH < 5.5, and at pH > 6
[V2 OL4 ] is the most abundant complex. We see that the high stability constants
Vanadium(III) Complexes with Picolinic Acid and Dipicolinic Acid in Aqueous Solution 913

for the [VL2 ]+ complexes compared to those of the [VL]2+ complexes (see
Table IV) indicate that these complexes form nearly simultaneously.(28)
The UV–vis spectra obtained for this system employing the condition B =
3 mM and R = 2 at different pH (Fig. 6) show the formation of an intense charge-
transfer band with two λmax at 501 and 627 nm, respectively. A similar behavior
can be observed in the literature for the complexes formed with histidine (L-
his) [V2 (L-his)4 (O)],(29,30) tetrapyridylamine (tpa) [{VBr(tpa)2 }2 O],(31) bypyridine
(bpy) [{VCl(bpy)2 }2 O]Cl2 ,(26) and phenantroline (phen) [{VCl(phen)2 }2 O]Cl2 .(27)
It is important to say that all these complexes have been well characterized by
UV-Vis, Raman spectroscopy and by X-ray crystallography. These results permit
us to confirm from the behavior observed in the electronic absorption spectra in
this work, together with the potentiometric results and consideration of the reports
obtained from the literature that the complex [V2 OL4 ] produced with picolinic
acid corresponds to a µ-oxo dimer complex.
For vanadium(III) dipicolinic acid, the potentiometric emf (H) data anal-
ysis showed the formation of the mononuclear complexes (Table VI): [VL]+ ,
[V(OH)L], [V(OH)2 L]− , [V(HL)(L)] and [VL2 ]− . If we compare the stability
constant of the [Vdipic]+ complex with that of the [Vpic]2+ complex:
V3+ + pic−
Vpic2+ log β = 6.01 ± 0.09
+
V 3+
+ dipic 2−

Vdipic log β = 8.41 ± 0.04
we can see that the stability constant of the [Vdipic]+ complex is higher than
the stability constant of [Vpic]2+ . It tells us that dipicolinic acid is coordinated
to the vanadium(III) by the nitrogen pyridine ring and the two oxygens from the
carboxylic groups act as a tridentade ligand. For this system the formation of two
hydroxo complexes were detected and are produced by the hydrolysis of the 1:1
vanadium(III) dipicolinic acid complex:
H2 O + VL+
V(OH)L + H+ pK a1 = 4.54 ± 0.04
− +
V(OH)L
V(OH)2 L + H pK a2 = 6.98 ± 0.04
Two complexes were detected with the stoichiometry vanadium(III):
dipicolinic acid, 1:2: a protonated [V(HL)(L)] complex and the [VL2 ]− com-
plex. Chatterjee et al.(7) synthesized and characterized different vanadium(III)
complexes with α-N-heterocyclic carboxylato NO donor ligands. They reported
the synthesis of one 1:1 V3+ dipicolinic acid complex, [V(dipic)(H2 O)2 F]·1.5H2 O,
and one protonated 1:2 V3+ dipicolinic acid complex, [V(dipic)(Hdipic)(H2 O)]·
3H2 O; in both cases the vanadium(III) complexes were hexacoordinated. Of
course, the [V(HL)(L)] complex has one dipicolinic acid acting as a tridentate
ligand with the second ligand is acting as a bidentate ligand, maintaining one
carboxylic group protonated and coordinated to the V(III) by (N,COO− ). The pKa
value for the reaction of [V(HL)(L)] to form [VL2 ]− is 2.81(4), indicating the
914 Lubes

deprotonation of the carboxylic group and the coordination to V(III).

V(HL)L
VL−
2 +H
+
−log β = 2.81 ± 0.04

In Fig. 5 is presented the species distribution diagram for this system at the
following conditions: (a) B = 3 mM, R = 1 and (b) B = 3 mM, R = 2. In the
first case, (Fig. 5a, the most important species is the complex [VL]+ , which
predominates in the pH range 1 < pH < 4.5, whereas at pH > 4.5 the [V(OH)L]
complex predominates; for this ratio, the V3+ dipicolinic acid potentiometric data
were collected at pH < 5 and at the metal ligand ratio 1:2. The potentiometric
measurement was made to pH ∼ 7.2, because precipitation of an insoluble material
occurred at these pH values in both cases. For the ratio R = 2 at pH = 1.8, the
[VL]+ and protonated [V(HL)L] complexes are presented in Fig. 5b. The [VL2 ]−
complex is the predominant species which is present in higher concentrations in
the pH range 3 < pH < 7 and the hydrolytic complexes are formed to a lesser
extent in the pH range 5 < pH < 7.
At the beginning of the titration, the mixture of V3+ -dipicolinic acid had a
yellow color in both cases (R = 1 and R = 2). This color became darker during
the titration of the acidic solutions with KOH.
The spectrophotometric measurements were made in order to obtain infor-
mation about the coordination of the vanadium(III) complexes. Figure 7 shows the
UV-Vis spectra for this system at the following condition B = 3 mM and R = 2.
An increasing of the band in the 400 nm region is observed when the acidic solu-
tion is titrated with KOH, and this band is attributed to the formation of hydrolytic
products.(25,32) It is interesting that for dipicolinic acid the formation of a dimeric
µ-oxodivanadium(III) complex is not observed, probably because of the higher
stability of the complexes formed with this ligand.

ACKNOWLEDGMENTS
I wish to thank the Decanato de Investigación y Desarrollo (DID) of the Uni-
versidad Simón Bolı́var (USB) (Project CB-011-03-PN (S1-2003)). I want to thank
Professor Felipe Brito from the Universidad Central de Venezuela (UCV) and Pro-
fessors Antonio Barriola, Antonio Zapata, Simón López, and Jorge Mostany from
the (USB).

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