Russian Journal of Coordination Chemistry, Vol. 30, No. 1, 2004, pp. 38–42. Translated from Koordinatsionnaya Khimiya, Vol.

30, No. 1, 2004, pp. 41–46.

Original Russian Text Copyright © 2004 by Shebaldina, Kovalchukova, Strashnova, Zaitsev, Ivanova.

Synthesis and Physicochemical Properties

of d- and f-Metal Complexes with Alloxan
L. S. Shebaldina*, O. V. Kovalchukova*, S. B. Strashnova*, B. E. Zaitsev*, and T. M. Ivanova**
* University of People’s Friendship, ul. Miklukho-Maklaya 6, Moscow, 117198 Russia
** Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, 119991
Received November 11, 2002

Abstract—Fifteen d- and f-metal complexes with alloxan were synthesized. Complexes of two types, in which
alloxan exists in mono- or diinozed form, were found to be formed, depending on the synthesis conditions (sol-
vents and pH of solutions). Physicochemical properties of alloxanates were studied by IR, X-ray photo electron,
and electronic absorption spectroscopies. The alloxan molecule was calculated using the PPP method. The
structures of complexes synthesized were suggested.

Pyrimidine oxo derivatives are heterocyclic com-
pounds are widely used, particularly, in medicine.
Thus, when studying their physiological effect on liv-
ing organisms, an increased content of oxo pyrimidines
was discovered in various tumor cells. 5,5-Dihydroxy-
2,4,6-trioxypyrimidine (alloxan, H2L) is capable of
influencing calcium, zinc, and phosphorus metabolism
in organisms and of increasing the blood sugar; there-
fore, it can be used in experimental studies of diabetes
[1]. Moreover, alloxan occurs in living organisms, and
is the product of uric acid decomposition [2].
A high biological activity of alloxan determines
considerable interest of scientists to its complexation
reactions. Thus, Co(II), Ni(II), and Cu(II) complexes
with alloxan, ML2 · 5H2O, were isolated from aqueous
alkaline solutions [3]; manganese(II) alloxanate was
obtained by evaporation of an acidified solvent at room
temperature [4]. As follows from spectrophotometric
data, cerium(III) forms with alloxan a soluble complex
ML2 [5]. Transition-metal salts are known to react with
alloxan solutions to give colored complexes: orange-
yellow or red for Cd(II), Mg(II), Cu(II), Zn(II), Co(II),
Ni(II), dark blue (in the presence of ammonia) for
Fe(II) [6]. The compositions and properties of Pb(II),
Hg(I), Hg(II), and Ag(I) alloxanates were not studied in
detail [6–9]. Previously [10, 11], we studied Fe(III) and
Co(III) complexes with alloxan; the synthesis of Co(II),
Ni(II), and Pd(II) alloxanates was also reported in [12].
The aim of this work was to study complexation of
a series of d and f metals with alloxan and to elucidate
regularities in compositions, structures, and properties
of complexes depending on the type of complexing
metal.
EXPERIMENTAL
Analytical grade crystal hydrates of cobalt(II) and
nickel(II) acetates, cadmium, zinc and palladium(II)
chlorides, scandium(III), lanthanum(III), praseody-
mium(III), europium(III), terbium(III), gadolin-
ium(III), and dysprosium(III) nitrates, and pure grade
ç2L trihydrate were used in the synthesizs.
Synthesis of ML · nH2O (M = Co (I), Ni (II), Pd
(III)) and M2L(An)2 · nH2O (M = Zn (IV), Cd (V),
An = Cl and OH, respectively). The relevant metal
salt (10–3 mol) was dissolved in 20–25 ml of water,
heated to boiling, and slowly mixed with an aqueous
solution containing 10–3 mol of ç2L in 20 ml. Thereaf-
ter, 2N NaOH was added in drops during 30 min to
bring pH to 8–8.5, and the reaction mixture was kept on
a water bath until crystallization began. After cooling,
polycrystalline precipitates were isolated, filtered off,
washed with ethanol, and dried in a desiccator over
ê2é5 to a constant mass. The yield was 40–50%.
Synthesis of Zn(HL)OH · 2H2O (VI) and
Cd(HL)Cl · 5H2O (VII) was carried out using similar
procedure, but the reaction mixture was preliminarily
evaporated to half a volume and then alkali was added.
Precipitates began to crystallize at pH 6. The yield was
46–50%.
Synthesis of complexes M(HL) 2 · n H 2O (M =
Co (VIII), Sc (IX), La (X), Pr (XI), Eu (XII)) and
ML(NO3) · nH2O (M = Tb (XIII), Gd (XIV), Dy
(XV)) was carried out by mixing hot neutral water–eth-
anol (50%) equimolar solutions of alloxan and the rel-
evant metal salt (c = 10–3 mol/l). The reaction mixture
was kept on a water bath at 60°ë for 2 h. The complexes
began to crystallize after partial evaporation of the sol-
vent. The polycrystalline precipitates formed were fil-
tered off, washed with a small amount of ethanol, and
dried in a desiccator over KOH to a constant mass. The
yield was 30–40%.
Chemical analysis for the metal ions was performed
using direct (Co2+, Ni2+, Zn2+, Cd2+) and back (Sc3+,
Ln3+) complexometric titration; nitrogen, carbon, and
chlorine were determined using microanalysis. The

1070-3284/04/3001-0038 © 2004 åÄIä “Nauka /Interperiodica”

 SYNTHESIS AND PHYSICOCHEMICAL PROPERTIES 39

Table 1. Chemical analysis data for d-metal complexes with alloxan

Content (found/calcd), %
Compound Empirical formula M, g/mol
M C N Cl

CoL · 7H2O (I) CoC4N2H16O12 343 16.70/17.18 14.70/14.00 8.40/8.16

NiL · 5H2O (II) NiC4N2H12O10 307 19.30/19.14 15.70/15.65 8.10/9.19
PdL (III) PdC4N2H2O5 264 41.10/40.24 18.20/18.15 11.10/10.59
Zn2L(OH)2 · 6H2O (IV) Zn2C4N2H14O12 412 32.91/33.03 11.54/12.14 7.26/7.07
Cd2LCl2 · 2H2O (V) Cd2C4N2H4O5Cl2 455 48.15/48.85 9.35/10.15 5.78/5.92 15.96/15.0
Zn(HL)OH · 2H2O (VI) ZnC4N2O7H6 259 25.34/25.19 18.30/18.52 10.73/10.79
Cd(HL)Cl · 5H2O (VII) CdC4N2H11O5Cl 314.5 28.05/28.65 13.79/13.67 7.39/7.41 8.87/9.36
Co(HL)2 · 6H2O (VIII) CoC8N4H18O16 485 12.30/12.14 20.50/19.80 11.80/11.55
Sc(HL)2NO3 · 7H2O (IX) ScC8N5H20O20 551 8.05/8.17 17.91/17.42 12.34/12.70
La(HL)2NO3 · 9H2O (X) LaC8N5H24O22 681 20.27/20.41 14.34/14.10 10.03/10.28
Pr(HL)2NO3 · 2H2O (XI) PrC8N5H10O15 557 25.82/25.31 17.40/17.24 12.01/13.57
Eu(HL)2NO3 · 5H2O (XII) EuC8N5H16O18 622 24.80/24.44 15.27/15.43 11.30/11.25
TbLNO3 · 2H2O (XIII) TbC4N3H6O10 415 37.98/38.31 11.38/11.57 10.22/10.12
GdLNO3 · 2H2O (XIV) GdC4N3H6O10 413 37.84/38.01 11.56/11.62 10.28/10.17
DyLNO3 · 9H2O (XV) DyC4N3H20O17 539 30.40/30.24 8.65/8.90 8.01/7.79

presence of the nitrate anions in the composition of
complexes was confirmed by qualitative reactions. The
chemical analysis data, empirical formulas, and com-
positions of complexes I–XV are presented in Table1.
Electronic absorption spectra of the ligand and com-
plexes in aqueous solutions and in the crystal form (pel-
lets with KBr) were recorded on a Specord UV-VIS
spectrophotometer in the range of 200–750 nm.
IR spectra of ç2L and crystal complexes I–XV were
taken on a Specord 75IR spectrophotometer in the
4000–400 cm–1 range.
X-ray photoelectron spectra of ç2L and complexes
I and VIII were recorded on an ES-100 instrument with
a magnesium anode. The ë1s (285.0 eV) line of hydro-
carbons of diffusion oil vapor was used as the standard.
pH-Potentiometric titration was carried out at 21°ë
using a laboratory pH-683 millivoltmeter; an ELS-43-
07 silver electrode was used as the indicator electrode,
and an EVL-1MZ silver chloride electrode was used as
the reference electrode. The ionization constant for the
ligand and the stability constants for complexes were
calculated using the Albert and Sergeant method [13].
Quantum-chemical calculations of tautomeric
forms of the alloxan molecule were carried out using
the Pariser–Pople–Parr (PPP) method (Dewar version)
[14].
RESULTS AND DISCUSSION
It is known that hydrated alloxan can potentially
exist in different tautomeric forms:

HO OH HO OH HO OH HO OH
O 5
O O O HO O HO O
4 6
1
HN 3 2 NH HN N N NH N N

O OH O OH
lactam monoenol I monoenol II dienol

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 1 2004

40 SHEBALDINA et al.

Table 2. Electronic absorption spectra of alloxan and its The calculated atomization heats (∆H) indicated
complexes with d metals that of all forms presented, monoenol II form is most
stable in the gas phase (∆H = 62.71 eV). Stabilities of
π π* n π* monoenol I, dienol, and lactam forms are somewhat
Solvent or pel- lower (∆H = 62.44, 62.64, and 62.65 eV, respectively).
Compound
lets with KBr λmax, nm
λmax, nm (logε) According to X-ray diffraction data [15, 16], the crystal
(logε)
alloxan molecule exists as the lactam (trioxo) form.
H2L H2O + EtOH 200–230 (4.14) 277 (2.32)
However, close intermolecular interaction energies for
above tautomers (4.86, 4.27, 4.53, and 5.22 eV) makes
H2L NaOH 228 (3.72) 264 (2.70) it possible to suggest that in solutions, several forms
exist simultaneously, and can be stabilized during com-
I H2O, strd <200 265 plexation.
III H2O, strd <200 264 The electronic absorption spectrum of alloxan in
IV KBr <200 264 50% water–ethanol solution exhibits an intense asym-
metric band in the range of 200–230 nm (logε = 4.14)
V KBr <200 266 due to the π–π* transitions of conjugated multiple
bands, as well as the low-intensity band at 277 nm (logε
VI KBr 220 261 = 2.32), which can be assigned to the n–π* transition of
VII KBr 220 264 the ketone groups [10]. These bands point to the pres-
ence of lactam form of the molecules in the solution.
VIII H2O, strd 225 265 When a solution of ç2L was alkalified with sodium
hydroxide to make 7 < pH < 11, the absorption band
IX KBr 225 265
appeared in the electronic spectrum at 264 nm, and
X KBr 225 262 isosbestic point was observed, presumably, due to the
enolic rearrangement of the molecule and the ioniza-
XI KBr 228 266 tion of the hydroxyl group in position 2 or 4 (according
XII KBr <200 265
to calculations, the ionization of hydroxyl group in
position 5 is less probable). Further increase in pH
XIII KBr <200 263 (≥12) leads to disclosure of the pyrimidine ring [2] as
demonstrated by irreversible change in the electronic
XV KBr <200 265 absorption spectrum.

Table 3. Absorption frequencies (cm–1) and assignment of selected bands in the IR spectra of alloxanates
Compound ν(NH) + ν(OH) ν(C(2)=O) ν(C(4)=O), ν(C(6)=O) νs(C(4)=O), νs(C(6)=O) ν(N=C–O) ν(NO3)
H2L 3360–3050 1777 1717 1695 shld
I 3370–3050 1675 1610
II 3370–3025 1690 1630
III 3600–3050 1683 shld 1645
IV 3300–3150 1690 1620
V 3400–3200 1700 1625
VI 3600–3000 1700 1680 1620
VII 3370–3000 1710 1690 shld 1620
VIII 3370–3050 1717 1695 shld 1620
IX 3600–3100 1715 1685 1625 1530, 1350
X 3600–3050 1715 1685 1625 1535, 1350
XI 3600–2900 1705 1670 1640 1550, 1360
XII 3500–2800 1705 1670 1630 1550, 1335
XIII 3550–3350 1640 1620 1545, 1355
XIV 3550–3300 1650 1620 1530, 1360
XV 3600–3400 1660 1615 1525, 1360

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 1 2004

 SYNTHESIS AND PHYSICOCHEMICAL PROPERTIES 41

The ionization constant (pKa) of alloxan calculated
from spectrophotometric data was 7.91.
The positions of long-wave bands in the electronic
absorption spectra of complexes are close to the posi-
tion of this band in the spectrum of the ionized ligand
(Table 2), which confirms that the ionized ligand is
coordinated to metals. For the complexes containing
the ligand in the twice deprotonated form (I–VIII,
XIII–XV), the maximum of the ligand band assigned to
the π–π* transition shifts towards the region below
200 nm.
The IR spectrum of crystal alloxan exhibits an
intense band due to the carbonyl vibrations: it has
poorly defined maxima at 1777 and 1715 cm–1 and a
shoulder at 1695 cm–1. Previously [10, 11], the band at
1777 cm–1 was assigned to the vibrations of the carbo-
nyl group in the alloxan amide fragment (–NH–CO–
NH–) and the band at 1715 cm–1 and the shoulder at
1695 cm–1, to asymmetric and symmetric vibrations of
two ketone groups in positions 4 and 6. In the range of
3360–3050 cm–1, broad intense bands due to overlap-
ping vibrations of the NH and OH groups were
observed.
When analyzing the IR spectra of complexes (Table
3), two groups of compounds can be distinguished. The
first group includes d-metal alloxanates isolated from
water–ethanol solutions at pH 6–7 and scandium and
light rare-earth (La, Pr, Eu) (VI–XII) alloxanates, in
which monoionized alloxan is coordinated to a metal.
In the spectra of these compounds, two bands of the
carbonyl groups in positions 4 and 6 (1715, 1695 cm–1)
remain unchanged, while the band at 1777 cm–1 disap-
pears. The absorption bands at 1550–1530 cm–1 and
1360–1335 cm–1 observed in the IR spectra of com-
plexes IX–XII are due to asymmetric and symmetric
stretching vibrations of nitrate anions coordinated in a
bidentate fashion [17]. The coordination sphere can be
completed owing to coordination of water molecules
and inorganic anions containied in the complex. Thus,
the structures of the first-type complexes can be pre-
sented by the following schemes:

H H2O H H2O O
O N O O N O OH
Cl(OH) 4 3 2 N OH
HO N M 5 1N M
HO
HO H2O HO N O
O O H2O O H
H2O
(VI, VII) (VIII)
O
H OH
O N O N OH
HO N M N O
O H
HO
O O O
N
O
(IX–XII)

The complexes of the second type include d-metal nal of the nitrogen atom of the C(NH)=O groups in
complexes isolated from alkaline solutions and heavy pyrimidines [18]. For the lactim form, the C(OH)=N
rare-earth (Tb(III), Gd(III), Dy(III)) complexes con- bond energy is equal to 399.1 eV, which is observed in
taining twice deprotonated alloxan molecules (I–V,
XIII–XV). In the IR spectra of these compounds, the
absorption bands at 1777 and 1715 cm–1 disappear, Table 4. Electron bond energies (eV) for alloxan and cobalt
alloxanates
while the absorption intensity in the range of 1650–
1550 cm–1 noticeably increases. The metal-chelate ring Compound N1s Co2p3/2
involving the carbonyl group in position 4 (or 6) can be
realized through both pyrimidine nitrogen atom and H2L 400.6
one of the hydroxyl groups in position 5, therefore, 401.1
X-ray photoelectron spectra of H2L and its cobalt com-
plexes (I, VIII) were studied in order to elucidate the I 400.6 782.6
coordination type. The spectrum of noncoordinated 399.5
H2L exhibits a broad N1s signal, which can be decom- VIII 400.6 782.6
posed into two components: 400.6 and 400.1 eV (Table 4).
The first value agrees with the literature data on the sig- 399.4

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 1 2004

42 SHEBALDINA et al.

Table 5. Stability constants for a series of alloxanates
Ion K1 × 10–3 K2 × 10–3 K1K2 × 10–6
Co2+ 4.34 0.65 2.85
Ni2+ 3.12 0.88 2.74
Sc3+ 2.71 1.05 2.84
La3+ 1.53 2.95 4.51
Tb3+ 1.52 2.70 4.10
Dy3+ 1.80 2.83 5.09
the spectra of complexes I and VIII, and, consequently,
the lactim form exists in both type complexes. At the
same time, in complex I, the N1s bond energy
(400.6 eV) for the second nitrogen atom does not
change, which makes it evident that only one nitrogen
atom is involved in the lactim rearrangement, while the
other one retains its lactam form. In connection with
this, a conclusion can be drawn that the alloxan dianion
is formed due to ionization of monoenol I form,
namely, the hydroxyl group in position 2 and one of the
hydroxyl groups in position 5. The five-membered
metal chelate ring formed ensures additional stabiliza-
tion of molecules. The bond energies for the ëÓ2p3/2
lines correspond to bivalent cations.
The presence of several water molecules in the inner
sphere of complexes was confirmed by thermogravi-
metric analysis (these data were reported previously in
[19]). Thus, for compound I, the dehydratation thermal
effects were observed at 98 (–2ç2é), 180 (–3ç2é), and
340°ë (–2ç2é) corresponding to absorption, crystalli-
zation, and coordination water molecules. Similar ther-
mograms were obtained for complexes II, IV, VII–X,
XII, which makes it possible to suggest the presence of
two to four water molecules in the inner sphere of com-
plexes.
The acidic–basic equilibrium of H2L and its reac-
tions with d-, and f-metal ions in water–ethanol solu-
tions were studied using the pH-metric titration
method. The curve for titration of H2L with alkali at pH
7–11 is typical of titration of weak monobasic acids.
The ionization constant of alloxan calculated for acidic
ionization in aqueous solution with the ionic strength
I = 2 (KNO3) at 20°ë is equal to Ka = 6.76 and differs
from the value calculated from spectrophotometric data
[19].
The titration curves for the alloxan–metal cation
mixture lie below similar curves for H2L. This fact can
be explained by the replacement of the ligand hydrogen
atom by a metal during complexation. The calculated
stability constants of a series of alloxanates are pre-
sented in Table 5.
REFERENCES
1. Bojarski, J.T., Mokrosz, J.L., and Paluchowska, M.N.,
Adv. Heterocycl. Chem., 1985, vol. 38, p. 229.
2. Comprehensive Organic Chemistry, Barton, D.H.R. and
Ollis, W.D., Eds., Pergamon, 1979, vol. 3.
3. Lange, W.E. and Foyc, W.O., J. Am. Pharm. Ass., 1956,
vol. 45, no. 3, p. 699.
4. Kharitonov, Yu. and Ambroladze, L.N., Koord. Khim.,
1983, vol. 9, no. 3, p. 424.
5. Saxena, M.C. and Bhattacharya, A.K., Z. Anorg. Allg.
Chem., 1962, vol. 315, no. 1, p. 114.
6. Deniges, G., Bull. Soc. Pharm. Bordeauk, 1991, vol. 3,
p. 161.
7. Deniges, G., J. Pharm. Chim., 1991, vol. 11, p. 530.
8. Resnik, R.A. and Cecil, H., Archives Biochem. Biophys.,
1956, vol. 61, p. 179.
9. Morel, A., Arloing, F., and Josserand, A. J. Anal. Chem.,
1949, vol. 52, no. 4, p. 674.
10. Kovalchukova, O.V., Gridasova, R.K., Zaitsev, B.E.,
et al., Zh. Neorg. Khim., 1981, vol. 26, no. 4, p. 985.
11. Leon Palomino, M.I., Gridasova, R.K., Zaitsev, B.E.,
and Kovalchukova, O.V., Zh. Neorg. Khim., 1981,
vol. 32, no. 10, p. 2583.
12. Koval’chukova, O.V., Molodkin, A.K., and Gridaso-
va, R.K., Zh. Neorg. Khim., 1983, vol. 28, no. 4, p. 1067.
13. Albert, A. and Serjeant, E., Ionization Constants, Lon-
don: Methuen, 1962.
14. Dewar, M., The Molecular Orbital Theory of Organic
Chemistry, New York: McGraw-Hill, 1969.
15. Mootz, D. and Jeffrey, G.A., Acta Crystallogr., 1965,
vol. 19, no. 4, p. 717.
16. Singh, C., Acta Crystallogr., 1965, vol. 19, no. 4, p. 759.
17. Palkina, K.K., Kuz’mina, N.E., Kovalchukova, O.V.,
et al., Zh. Neorg. Khim., 2000, vol. 45, no. 4, p. 586.
18. Nefedov, V.I. Rentgenoelektronnaya spektroskopiya
khimicheskikh soedinenii (X-Ray Electron Spectroscopy
of Chemical Compounds), Moscow: Khimiya, 1984.
19. Kovalchukova, O.V., Molodkin, A.K., Gridasova, R.K.,
and Vychuzhanin, V.A., Zh. Neorg. Khim., 1985, vol. 30,
no. 12, p. 3134.

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 1 2004