Poster presentation
66
INTERACTION OF TETRA-µ-FORMIATO-DIMOLYBDENUM
MONOHYDRATE WITH A POLYDENTATE DONOR BASE
Akhmedov Eldar Latif, Huseynguliyeva Kenul Fada, Akberova Saida Shamil
Azerbaijan Medical University, Department of Pharmaceutical Toxicology and
Chemistry, Baku
Previously, we found that the tetra-µ-carboxylate complex of dimolybdenum, in
particular, Mo
2
(O
2
CH)
4
H
2
O, is capable of
forming complexes of the Mo
2
(O
2
CH)
4
L
2
type (L are organic bases). Introduction of donor bases into axial positions leads, in
comparison with the initial complex, to more noticeable changes in the values of
ν(MoMo), ν
s
(MoO), ν
as
(COO), and ν
s
(COO) in the spectra of Mo
2
(O
2
CH)
4
L
2
-type
complexes. In
continuation of the research, it is advisable to obtain complexes of the
Mo
2
(O
2
CH)
4
L
2
type, where L is 4-aminopyridine (4-NH
2
Py). When carrying out the
reaction of Mo
2
(O
2
CH)
4
H
2
O with the indicated donor base, the task was also
to study
the preferred methods for coordinating axial ligands.
In the case of 4-NH
2
Py, two modes of coordination are possible: through the nitrogen
atom of the amino group Mo-N (amine), or through the nitrogen atom of the heterocycle
Mo-N (pyridine).
In the IR spectra of Mo
2
(O
2
CH)
4
(4-NH
2
Py)
2
there are intense absorption bands with
maxima near 3475 and 3375, 3230 cm
-1
. We assigned them to asymmetric and
symmetric stretching vibrations of the amino group of 4-aminopyridine. The
corresponding frequencies are increased compared to ν(NH
2
) of uncoordinated 4-
aminopyridine by 31-60 cm
-1
, i.e. in the 4-NH
2
Py molecule, the donor nitrogen atom of
the NH
2
groups does not participate in the
bond with the molybdenum atom, since
otherwise, the frequencies of stretching vibrations ν(NH
2
) of the amino group would
have to decrease significantly. The absorption band of the bending scissor vibrations of
the amino group in the region of 1655 cm
–1
practically does not shift.
Thus, 4-aminopyridine forms a bond with molybdenum in Mo
2
(O
2
CH)
4
(4-NH
2
Py)
2
through the nitrogen atom of the pyridine ring, which is consistent with an increase in
the frequencies of the stretching vibrations of the ring in the region of 1500-1600 and
1000-1100 cm
-1
by 10-30 cm
-1
. These data are consistent with the stoichiometric rules,
according to which the closure of the metallocycle through
the functional groups of
cyclic ligands located in the β-position relative to each other is very difficult, and in the
γ-position it is almost impossible.
Thus, the study of the spectral characteristics of the Mo
2
(O
2
CH)
4
(4-NH
2
Py)
2
complexes showed that the nitrogen atom of the heterocycle has more efficient donor
properties than the nitrogen atom of the amino group located in the para position to the
nitrogen atom of the heterocycle.
In the region 400-500 cm
-1
in the IR spectrum of Mo
2
(O
2
CH)
4
(4-NH
2
Py)
2
three
intense absorption bands were found with maxima at about 435, 440 and 464 cm
-1
; the
first two absorption bands, which are inactive in the Raman spectra, are also present in
the spectrum
of the initial complex, Mo
2
(O
2
CH)
4
H
2
O, which gives reason to attribute
them to asymmetric stretching vibrations of the Mo–O bonds.