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Vanadium (III) Complexes With Picolinic Acid and Dipicolinic Acid in Aqueous Solution
Vanadium (III) Complexes With Picolinic Acid and Dipicolinic Acid in Aqueous Solution
8, August 2005 (
C 2005)
DOI: 10.1007/s10953-005-6253-8
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.
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
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.
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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
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
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)
and the ratio R = 2; and (b) B = 0.003 mol-dm−3 and the ratio R = 10.
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 )
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.
V (mL) E (mV) V (mL) E (mV) V (mL) E (mV) V (mL) E (mV) V (mL) E (mV) V (mL) E (mV)
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
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.
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. 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
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).
REFERENCES
1. K. A. Idriss, M. S. Saleh, H. Sedaira, M. M. Seleim, and E. Y. Hashem, Monatsh. Chem. 122, 507
(1991).
2. C. G. Pope, E. Matijecic, and R. C. Pate, J. Colloid Interface Sci. 80, 74 (1981).
3. A. M. Lannon, A. G. Lappin, and M. G. Segal, Inorg. Chem. 23, 4167 (1984).
Vanadium(III) Complexes with Picolinic Acid and Dipicolinic Acid in Aqueous Solution 915
4. AMBI Inc., Press release: http://blz/yahoo.com/bw/990326/ny ambi 1/html AMBI Inc. Website:
http://www.AMBInc.com,1999.
5. R. A. Anderson, Diabetes Metab. 26, 22 (2000).
6. T. E. Erikson, I. Grenthe, and I. Puigdomenech, Inorg. Chim. Acta 126, 131 (1987); Y. Ducommun,
L. Helm, G. Laurenezy, and A. Merbach, Inorg. Chim. Acta 158, 3 (1989).
7. M. Chatterjee, M. Maji, S. Ghosh, and T. C. W. Mak, J. Chem. Soc., Dalton Trans. 3641 (1998).
8. R. C. Mercier and M. R. Pâris, Bull. Soc. Chim. France 3577 (1965).
9. M. Chatterjee, S. Ghosh, and A. K. Nandi, Polyhedron 16, 2917 (1997).
10. M. Melchior, S. J. Rettig, B. D. Liboiron, K. H. Thompson, V. G. Yuen, J. H. McNeill, and C.
Orvig, Inorg. Chem. 40, 4686 (2001).
11. K. H. Thompson and C. Orvig, Coord. Chem. Rev. 219–221, 1033 (2001).
12. M. Melchior, K. H. Thompson, J. M. Jong, S. J. Rettig, E. Shuter, V. G. Yuen, Y. Zhou, J. H.
McNeill, and C. Orvig, Inorg. Chem. 38, 2288 (1999).
13. A. E. Martell, M. Smith, and R. J. Motekaitis, NIST Critical Stability Constants of Metal Complexes
Database (US Department of Commerce, Gaithersburg, MD, 1993); K. J. Powell and L. D. Pettit,
IUPAC Stability Constants Database (Academic Software, Otley, UK, 1997).
14. F. Brito, An. Fis. Quı́m. B 62, 193 (1966).
15. S. Mateo and F. Brito, An. Fis. Quı́m. B 64, 115 (1968).
16. F. Brito and J. M. Goncalves, An. Fis. Quı́m. 78, 104 (1982).
17. G. Biedermann and L. G. Sillén, Arkiv Kemi 5, 425 (1952).
18. V. Lubes, Complejos de V(III) y los Ácidos Aminopolicarboxı́licos NDAP, NADP y NTP (25 ◦ C,
KCl 3.0 M), Tesis de Licenciatura, Facultad de Ciencias, UCV, 1997.
19. F. Brito and J. Goncalves, Proyecto no S1-1228 (CONICIT. Caracas, Venezuela, 1981).
20. R. Arnek, L. G. Sillén, and B. Warnqvist, Arkiv Kemi 31, 341 (1969).
21. L. Alderighi, P. Gans, A. Ienco, D. Peters, A. Sabatini, and A. Vacca, Coord. Chem. Rev. 184, 311
(1999).
22. S. Funahashi, K. Haraguchi, and M. Tanaka, Inorg. Chem. 16, 1349 (1977).
23. B. Szpoganicz and A. Martell, Inorg. Chem. 23, 4442 (1984).
24. D. C. Crans, J. J. Smee, E. Gaidamauskas, and L. Yang, Chem. Rev. 104, 849 (2004).
25. K. Kanamori, Coord. Chem. Rev. 237, 147 (2003).
26. S. G. Brand, N. Edelstein, C. J. Hawkins, G. Shalimo, M. R. Snow, and R. T. Tiekink, Inorg. Chem.
29, 434 (1990).
27. H. Kumagai, S. Kitagawa, M. Maekawa, S. Kawata, H. Kiso, and M. Munakata, J. Chem. Soc.,
Dalton Trans. 2390 (2002).
28. J. Piispanen and L. H. J. Lajunen, Acta Chem. Scand. 50, 1074 (1996).
29. K. Kanamori, M. Teraoka, H. Maeda, and K. Okamoto, Chem. Lett. 1731 (1993).
30. K. Bukietynska, Z. Karwecka, and H. Podsiadly, Polyhedron 16, 2613 (1997).
31. K. Kanmori, E. Kameda, T. Kabetani, T. Suemoto, K. Okamoto, and S. Kaizaki, Bull. Chem. Soc.
Jpn. 68, 2581 (1995).
32. H. Maeda, K. Kanamori, H. Michibata, T. Cono, K. Okamoto, and J. Hidaka, Bull. Chem. Soc.
Jpn. 66, 790 (1993).