20
AFANAS’EVA et al.
tions
(Au–Cl) appear at 356 cm–1 [AuCl2]– and at 365
ν
and 355 cm [AuCl4]–, respectively [28].
–1
Au(1)
Halogenation of the sixꢀmembered chelate rings at
the
the IR spectra of the complexes: the band at 3085 cm
(СН) observed for complexes I, IV, and disappears
in the spectra of ꢀchlorinated and ꢀbrominated
complexes II III, and VI–IX; the number of bands at
60–770 (outꢀofꢀplane vibrations (CH) mixed with the
skeletal vibrations of the ligand) and 1560–1526 cm
βꢀcarbon atoms produces the following changes in
–
1
ν
V
O(2)′
β
β
O(6)
′
Cl(1)
′
O(8)
,
O(1)
8
γ
Cl(2)
′
O(7)
′
Cl(2)
O(7)
–1
Cl(1)
(ring vibrations) decreases. Earlier, similar effects have
been observed for halogenated acetylacetonates [29].
O(8)
′
O(2)
1
The H NMR spectra of the chlorinated complexes
+
+
[
AuA(Cl)]2 and [AuB(Cl)2] show no signals for the
Au(1)
′
CH groups (Table 5), in contrast to the spectra of the
starting complexes [AuA]2 and [AuB] , because the
+
+
hydrogen atoms at the central ꢀcarbon atoms of the
β
sixꢀmembered rings are displaced by the chlorine
atoms.
y
REFERENCES
O(1w)′
1
. Yatsimirskii, K.B., Kolchinskii, A.G., Pavlishchuk, V.V.,
and Talanova, G.G., Sintez makrotsiklicheskikh soedineꢀ
nii (Synthesis of Macrocyclic Compounds), Kiev:
Naukova Dumka, 1987.
2
. Gerbeleu, N.V. and Arion, V.B., Templatnyi sintez makꢀ
rotsiklicheskikh soedinenii (Template Synthesis of Macꢀ
rocyclic Compounds), Kishinev: Shtiintsa, 1990.
3
4
5
.
Coordination Chemistry of Macrocyclic Compounds,
Melson, G.A., Ed., New York: Plenum, 1979.
. Block, B.P. and Bailar, J.C., J. Am. Chem. Soc., 1951,
Fig. 10. Fragment of the cationꢀanionic chain in structure XII
.
vol. 73, no. 10, p. 4722.
. Brawner, S.A., Lin, I.J.B., Kim, J.ꢀH., and
Everett, G.W., Inorg. Chem., 1978, vol. 17, no. 5,
p. 1304.
ducing chains aligned with the short axis and extendꢀ
ing the coordination polyhedron of gold to a distorted
octahedron (Fig. 9). The dihydroxonium (X) and
hydroxonium cations (XII) alternate in these chains with
the gold(III) cations and are linked by short hydrogen
bonds with the perchlorate anions (O–H⋅⋅⋅O, 2.666(7)
6
7
8
. Kim, J.ꢀH. and Everett, G.W., Inorg. Chem., 1979,
vol. 18, no. 11, p. 3145.
. Afanas’eva, V.A., Mironov, I.V., Glinskaya, L.A., et al.,
Zh. Strukt. Khim., 2003, vol. 44, no. 1, p. 83.
. Afanas’eva, V.A., Glinskaya, L.A., Klevtsova, R.F.,
(
X
) and 2.566(6) Å (XII)) (Fig. 10).
et al., Zh. Strukt. Khim., 2007, vol. 48, no. 2, p. 296
1
[J. Struct. Chem. (Engl. Transl.), vol. 48, no. 2, p. 289].
9. Afanas’eva, V.A., Glinskaya, L.A., Klevtsova, R.F.,
IR and H NMR spectra. The IR spectra of the
complexes show bands at 570–400 cm–1 (Au–N
stretches, [28]). In the IR spectra of acyclic complexes
et al., Zh. Strukt. Khim., 2005, vol. 46, no. 5, p. 902.
1
0. Afanas’eva, V.A., Glinskaya, L.A., Klevtsova, R.F., and
Mironov, I.V., Zh. Strukt. Khim., 2005, vol. 46, no. 5,
p. 909.
I
1
–
III, the bands at 3264–3120
ν(N–H) and 1595–
–1
592 cm
δ
(NH2) are due to the vibrations of the
⎯
⋅⋅⋅
11. Afanas’eva, V.A., Mironov, I.V., Glinskaya, L.A., et al.,
coordinated NH groups. The delocalized
С
С
and
2
Zh. Strukt. Khim., 2004, vol. 45, no. 6, p. 1059.
⎯
С
⋅⋅⋅
520 cm (
tonated complex XI also contains the bands at
N bonds of the iminate rings absorb at 1560–
1
2. Afanas’eva, V.A., Glinskaya, L.A., Klevtsova, R.F., and
Sheludyakova, L.A., Zh. Strukt. Khim., 2005, vol. 46,
no. 1, p. 133.
–1
1
I–IX, XI). The IR spectrum of monoproꢀ
–1
1
680 cm (localized double С=N bond). The specꢀ 13. Ginzburg, S.I., Gladyshevskaya, K.A., Ezerskaya, N.A.,
trum of diprotonated complex XII shows an intense band
et al., Rukovodstvo po khimicheskomu analizu platiꢀ
novykh metallov i zolota (Handbook for the Chemical
Analysis of Platinum Metals and Gold), Moscow:
Nauka, 1965.
–1
–1
at 1670 cm
ν(С=N) and a shoulder at ~1600 cm
(
oxonium ion), while the bands due to the delocalized
⎯
С
⋅⋅⋅
N bonds are absent. In the spectra of complexes
1
4. Suslennikova, V.M. and Kiseleva, E.K., Rukovodstvo po
VII and VIII, the bands corresponding to the vibraꢀ
prigotovleniyu titrovannykh rastvorov (Manual on the
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 36
No. 1
2010