Reactions of aqueous copper acetate with triethylamine and 3,5-dimethylpyrazole

Article abstract of DOI:10.1134/S0036023610050104

The dissolution of aqueous copper acetate in tetrahydrofuran gives the Cu₂(μ-OOCMe)₄(thf)₂ complex (1), and its reaction with triethylamine in the presence of acetic acid yields {[Cu ₂(μ-OOCMe)₄[μ-OOC

Full text of DOI:10.1134/S0036023610050104

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2010, Vol. 55, No. 5, pp. 714–726. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © E.V. Perova, M.A. Yakovleva, E.O. Baranova, I.V. Anan’ev, S.E. Nefedov, 2010, published in Zhurnal Neorganicheskoi Khimii, 2010, Vol. 55, No. 5,
pp. 768–780.
COORDINATION COMPOUNDS
Reactions of Aqueous Copper Acetate with Triethylamine
and 3,5ꢀDimethylpyrazole
E. V. Perova, M. A. Yakovleva, E. O. Baranova, I. V. Anan’ev, and S. E. Nefedov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
eꢀmail: snef@igic.ras.ru
Received September 12, 2009
Abstract—The dissolution of aqueous copper acetate in tetrahydrofuran gives the Cu (µꢀOOCMe) (thf)
2
4 2
4
complex (
OOCMe(HNEt )]}n polymer
Cu(Hdmpz) (OOCMe) (
1
), and its reaction with triethylamine in the presence of acetic acid yields {[Cu (
µ
ꢀOOCMe) [µꢀ
2
(
2
). Complexes
and Cu ( ꢀOOCMe) (Hdmpz) (4)
2
1
4
and
4 0.5C H (5) are determined by Xꢀray diffraction.
6 6
2
react with 3,5ꢀdimethylpyrazole to form
3
3
)
µ
, respectively. The structures of complexes
2
2
2
1
–4
and that of solvate
×
DOI: 10.1134/S0036023610050104
Studies of the specific features of 3,5ꢀdimethylꢀ substituent R in the carboxylate anion in addition to
the nature of the transition metal.
pyrazole (Hdmpz) deprotonation in the presence
of M2(
ꢀOOCBut)4(NEt3)2 (M = Zn, Cu, Ni, Co)
showed that, depending on the transition metal
either the binuclear pyrazolateꢀbridged complexes
M2(
ꢀdmpz)2(Hdmpz)2(OOCBut)2 (M = Zn, Co)
or a mixture of the monoꢀ and binuclear comꢀ
plexes and
M(OOCBut)2(Hdmpz)2
M2(
ꢀOOCBut)4(Hdmpz)2 (M = Ni, Cu) were
μ
Such simple biꢀ and trinuclear pyrazolateꢀbridged
transition metal complexes can be suitable starting
reactants and/or intermediates in the formation of
more complicated polynuclear compounds and clusꢀ
ters up to pyrazolateꢀbridged organometallic polymers
suspected of having unusual magnetic, catalytic, and
electronꢀoptical properties [9–12].
,
μ
μ
formed under the same conditions [1–5]. Unlike the
binuclear nickel complex, the copper complex conꢀ
tains intramolecular hydrogen bonds of the NH
fragments of coordinated pyrazole and the oxygen
atoms of one bridging pivalate anion, which makes
it possible to deprotonate pyrazole during thermoꢀ
lysis to form a pyrazolate–pivalate bridged polymer,
This work concerns synthetic approaches to the
preparation of complexes based on copper acetate by
reactions with triethylamine and 3,5ꢀdimethylpyraꢀ
zole and features of their structure and hydrogen
bonding compared to analogous reactions of binuclear
copper pivalate.
whose reaction with Hdmpz yields the Cu2(
μ
ꢀ
dmpz)2(Hdmpz)2(OOCBut)2
pyrazolateꢀbridging
EXPERIMENTAL
dimer [2]. No pyrazolate anions were observed in the
thermolysis products of the binuclear nickel complex
[6]. The change in the nature of substituent R in the
carboxylate anion on going to the less donating aceꢀ
tate anion results in the formation of the pyrazolateꢀ
All procedures on the synthesis and isolation of the
complexes were carried out under pure argon using
anhydrous solvents.
IR spectra were recorded with Specord Mꢀ80 and
NexusꢀNicolet spectrophotometers as KBr pellets in
the frequency range 400–4000 cm–1.
bridged
dmpz)2(Hdmpz)2(OOCMe)2 and the trinuclear cobalt
complex Co2( ꢀdmpz)4(Hdmpz)2(OOCMe)2 upon
binuclear
zinc
complex Zn2(
μꢀ
μ
Xꢀray diffraction studies were performed according
to a standard procedure on a Bruker SMART Apex II
automated diffractometer equipped with a CCD
the interaction of the reaction products of aqueous
zinc and cobalt acetates and triethylamine with
Hdmpz [7, 8]. Thus, the earlier studies showed that the
composition, structure, and tendencies of intraꢀ and
intermolecular hydrogen bonding in the pyrazolateꢀ
and 3,5ꢀdimethylpyrazolateꢀbridged biꢀ and trinuꢀ
detector (λMo radiation, graphite monochromator,
ω
scan mode). The structures were calculated using the
SHELXTL PLUS program package (PC version). The
structures were refined using the SHELXTLꢀ97 proꢀ
clear complexes are dictated by the donor ability of gram package [13, 14].
714

REACTIONS OF AQUEOUS COPPER ACETATE
715
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 5 2010

716
PEROVA et al.
Table 2. Coordinates of atoms (×104) and equivalent isotropic
factors (×103, Å2) for complex 1
Synthesis of Cu2( ꢀOOCMe)4(THF)2 (1). Aqueous
μ
copper acetate (0.1 g, 0.5 mmol) was dissolved in tetꢀ
rahydrofuran (THF) on reflux. The resulting blue
solution was cooled to room temperature and kept for
24 h at –5°С. The dark blue crystals formed, which
rapidly decomposed at room temperature, were sepaꢀ
Atom
x
y
z
Ueq
Cu(1)
O(1)
O(2)
O(3)
O(4)
O(5)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
555(1)
1070(2)
103(2)
4008(1)
5205(4)
6930(4)
4971(4)
426(1)
–42(4)
11(1)
23(1)
22(1)
20(1)
22(1)
16(1)
16(1)
27(1)
18(1)
25(1)
27(1)
27(1)
30(1)
20(1)
rated from the mother liquor by decantation at 0°С
.
–797(4)
2038(3)
Synthesis of Cu2( ꢀOOCMe)4( ꢀ
μ
η
1230(2)
–273(2)
1426(2)
760(3)
OC(Me)OHNEt3)2 (2). Acetic acid (0.028 mL) was
added to a suspension of aqueous copper acetate (0.1 g,
0.5 mmol) in acetonitrile (15 mL), and the mixture
was stirred to complete dissolution. A triethylamine
excess (0.4 mL, 2.88 mmol) was added to the solution,
and a light green precipitate was formed. The reaction
mixture was heated for 1 h at 80°С until the precipitate
dissolved completely. The green solution obtained was
concentrated to 7 mL and kept for 24 h at +5°С. The
green crystals formed were separated from the mother
liquor by decantation. The yield was 0.111 g (64.8%).
3310(4) –1290(4)
2204(4)
6366(6)
7161(6)
6082(5)
6735(6)
948(5)
1092(3)
–555(5)
–901(6)
2156(6)
3444(5)
354(6)
1204(3)
967(3)
1544(3)
1054(4)
1492(3) –222(6)
1280(6)
2443(6)
2408(5)
1702(4)
1971(3)
411(6)
1860(6)
For C24H50N2O12Cu2 anal. calcd. (%): C, 42.04; H,
7.35; N, 4.09.
Found (%): C, 41.03; H, 7.03; N, 3.86.
The crystallographic data and refinement details
are given in Table 1. The coordinates of atoms and
selected geometric parameters of the complexes studꢀ
ied are listed in Tables 2–11.
IR (KBr), cm–1: 3731 w, 3438 s. br, 2937 w, 2739 w,
2678 w, 2491 w, 1631 s, 1565 s, 1430 s, 1344 w, 1048 s,
795 m, 682 m, 625 w, 467 s, 434 w.
Table 3. Selected bond lengths (d) and bond angles (ω) for complex 1
Bond , Å
d
Bond
Cu(1)–O(3)
d, Å
Cu(1)–O(1)
1.959(4)
1.953(4)
2.214(3)
1.967(4)
1.959(4)
1.967(4)
2.5868(12)
Cu(1)–O(4)
Cu(1)–O(5)
O(2)–Cu(1)#1
Cu(1)–O(2)#1
Cu(1)–Cu(1)#1
Angle
ω, deg
Angle
ω, deg
O(1)Cu(1)O(3)
89.57(17)
169.70(15)
89.23(16)
98.28(15)
92.97(14)
84.80(11)
84.37(11)
175.93(9)
121.5(3)
O(1)Cu(1)O(4)
89.94(17)
170.15(15)
89.50(17)
97.28(14)
91.57(15)
85.35(11)
85.35(11)
123.0(3)
O(3)Cu(1)O(4)
O(1)Cu(1)O(2)#1
O(4)Cu(1)O(2)#1
O(3)Cu(1)O(5)
O(3)Cu(1)O(2)#1
O(1)Cu(1)O(5)
O(4)Cu(1)O(5)
O(2)#1Cu(1)O(5)
O(3)Cu(1)Cu(1)#1
O(2)#1Cu(1)Cu(1)#1
C(1)O(1)Cu(1)
O(1)Cu(1)Cu(1)#1
O(4)Cu(1)Cu(1)#1
O(5)Cu(1)Cu(1)#1
C(1)O(2)Cu(1)#1
C(3)#1O(4)Cu(1)
C(3)O(3)Cu(1)
121.7(3)
123.3(4)
Note: Symmetry transformations used for the generation of equivalent atoms: #1 –x, –y + 1, –z.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 5 2010

REACTIONS OF AQUEOUS COPPER ACETATE
717
Table 4. Coordinates of atoms (×104) and equivalent isotropic factors (×103, Å2) for complex 2
Atom
x
y
z
Ueq
Atom
x
y
z
Ueq
Cu(1)
Cu(2)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
O(10)
N(1)
N(2)
C(1)
C(2)
5189(1) 10140(1)
5162(1) 10093(1)
5669(1) 11709(1)
9301(1)
5754(1)
9660(1)
9152(1)
9042(1)
9770(1)
8202(1)
6972(1)
5676(1)
5605(1)
5751(1)
5531(1)
2342(1)
2673(2)
14(1)
13(1)
20(1)
22(1)
25(1)
18(1)
18(1)
17(1)
19(1)
19(1)
19(1)
21(1)
16(1)
54(1)
18(1)
26(1)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
2992(2) 10693(2)
1795(2) 11069(2)
5219(2) 10500(2)
4221(2) 11310(2)
9529(1)
9241(1)
7523(1)
7350(1)
5021(1)
4987(1)
5141(1)
5217(1)
2873(1)
3340(1)
1793(1)
1315(1)
1924(1)
2438(1)
2654(1)
2631(1)
16(1)
21(1)
12(1)
23(1)
16(1)
22(1)
18(1)
23(1)
24(1)
32(1)
24(1)
34(1)
25(1)
31(1)
31(1)
27(1)
4659(1)
3612(1) 10657(1)
6709(1) 9563(1)
8520(1)
3065(2)
1888(2)
5879(2)
6411(2)
9170(2)
8739(2)
7998(2)
6809(2)
5604(1) 10209(1)
5654(1) 10148(1)
3652(1)
6608(1) 10752(1)
5792(1) 8513(1)
9416(1)
2108(2) 12082(2)
1511(2) 11279(2)
1960(2) 10652(2)
955(2) 11244(2)
3315(2) 12299(2)
4338(2) 12805(2)
8054(2) 10764(2)
7072(2) 11483(2)
4436(1) 11609(1)
2716(1) 11454(1)
8811(2) 10184(2)
5682(2) 12058(2) 10334(1)
6156(2) 13246(2) 10549(1)
Table 5. Selected bond lengths (d) and bond angles (ω) for complex 2
Bond , Å
Cu(1)–O(1)
d
Bond
Cu(1)–O(3)
Cu(1)–O(4)
d, Å
1.9672(14)
1.9755(14)
2.1125(13)
1.9620(14)
1.9768(13)
2.1249(13)
1.9729(15)
1.9839(14)
2.6339(5)
1.9756(14)
1.9834(14)
2.6366(5)
Cu(1)–O(2)
Cu(1)–O(5)
Cu(2)–O(10)
Cu(2)–O(9)
Cu(2)–O(6)
Cu(1)–Cu(1)#1
Cu(2)–O(7)
Cu(2)–O(8)
Cu(2)–Cu(2)#2
Angle
ω, deg
Angle
ω, deg
O(1)Cu(1)O(3)
O(3)Cu(1)O(2)
O(3)Cu(1)O(4)
O(1)Cu(1)O(5)
O(2)Cu(1)O(5)
O(1)Cu(1)Cu(1)#1
O(2)Cu(1)Cu(1)#1
O(5)Cu(1)Cu(1)#1
O(10)Cu(2)O(9)
O(10)Cu(2)O(8)
O(9)Cu(2)O(8)
O(7)Cu(2)O(6)
O(8)Cu(2)O(6)
O(7)Cu(2)Cu(2)#2
O(8)Cu(2)Cu(2)#2
C(1)O(1)Cu(1)
C(3)O(3)Cu(1)
C(5)O(5)Cu(1)
C(7)O(7)Cu(2)
C(9)O(9)Cu(2)
90.52(6)
88.73(6)
168.42(6)
98.89(6)
92.51(5)
84.49(4)
84.05(4)
173.93(4)
168.27(6)
90.45(6)
89.81(6)
98.68(5)
92.77(5)
87.14(4)
81.40(4)
123.18(13)
122.75(13)
142.12(13)
119.78(13)
122.48(13)
O(1)Cu(1)O(2)
O(1)Cu(1)O(4)
O(2)Cu(1)O(4)
O(3)Cu(1)O(5)
168.53(6)
88.94(6)
89.50(6)
100.15(6)
91.37(5)
84.81(4)
83.62(4)
87.88(6)
89.54(6)
168.53(6)
101.67(6)
90.03(5)
84.15(4)
84.29(4)
171.86(4)
123.11(13)
123.50(13)
135.88(13)
126.37(14)
123.36(13)
O(4)Cu(1)O(5)
O(3)Cu(1)Cu(1)#1
O(4)Cu(1)Cu(1)#1
O(10)Cu(2)O(7)
O(7)Cu(2)O(9)
O(7)Cu(2)O(8)
O(10)Cu(2)O(6)
O(9)Cu(2)O(6)
O(10)Cu(2)Cu(2)#2
O(9)Cu(2)Cu(2)#2
O(6)Cu(2)Cu(2)#2
C(1)#1O(2)Cu(1)
C(3)#1O(4)Cu(1)
C(5)O(6)Cu(2)
C(7)#2O(8)Cu(2)
C(9)#2O(10)Cu(2)
Note: Symmetry transformations used for the generation of equivalent atoms: #1 –x + 1, –y + 2, –z + 2; #2 –x + 1, –y + 2, –z + 1.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 5 2010

718
PEROVA et al.
C(4)
C(3)
O(4A)
O(3)
C(8)
C(2)
O(2)
C(5A)
C(1)
O(1)
C(7)
C(6)
O(5)
C(6A)
C(7A)
Cu(1)
C(1A)
O(2A)
Cu(1A)
O(5A)
O(1A)
C(2A)
C(5)
C(8A)
O(3A)
O(4)
C(3A)
C(4A)
Fig. 1. Structure of complex 1.
C(8A)
O(4A)
C(14)
C(13)
C(7A)
O(7A)
O(10A)
C(11)
C(6A)
C(12)
C(3A)
O(4)
O(3A)
Cu(2A)
O(6A)
N(1)
C(16)
C(15)
C(10)
C(5A)
O(5A)
O(1A)
C(2A)
O(2)
H(1A)
C(1A)
Cu(1A)
O(8A)
C(9)
O(9)
O(2A)
O(9A)
C(9A)
C(10A)
Cu(1)
H(1AA)
C(1)
C(16A)
O(5)
C(5)
O(8)
O(1)
C(2)
N(1A)
O(6)
O(4A)
C(13A)
C(12A)
C(11A)
Cu(2)
C(15A)
O(3)
C(3)
C(6)
C(7)
O(7)
C(4)
C(14A)
O(10)
C(8)
Fig. 2. Structure of complex 2.
Synthesis of Cu(Hdmpr)2(OOCMe)2 (3) and green crystals of complex
4
were separated from the
mother liquor by decantation and isolated mechanꢀ
Cu2( ꢀOOCMe)4(Hdmpz)2 (4). (a) Complex 1
μ
ically under a microscope. The yield of complex
was 0.005 g (10%).
3
(0.1 g, 0.2 mmol) in THF (5 mL) was added to a
solution of 3,5ꢀdimethylpyrazole (0.051 g,
0.53 mmol) in THF (5 mL), and the mixture was
stirred at 40°С for 1 h. The resulting blueꢀgreen
solution was concentrated to 7 mL and kept for 24 h
For C14H22N4O4Cu anal. calcd. (%): C, 44.97; H,
5.93; N, 14.98.
at +5°С. The blue crystals of complex
3
and the
Found (%): C, 45.61; H, 5.88; N, 15.11.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 5 2010

REACTIONS OF AQUEOUS COPPER ACETATE
719
Table 6. Coordinates of atoms (×104) and equivalent isotropic
factors (×104, Å3) for complex 3
IR (KBr), ν, cm–1: 3452 m.br, 3181 w, 3090 w, 3029
w, 2976 w, 2870 w, 2777 w, 1554 s, 1431 s, 1343 w, 1307
m, 1181 w, 1152 w, 1082 w, 1025 m, 939 m, 833 m, 677
m, 622 w, 589 w, 473 m.
Atom
x
y
z
Ueq
Cu(1)
O(1)
O(2)
O(3)
O(4)
N(1)
N(2)
N(3)
N(4)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
9049(1)
7291(4)
8258(4)
8119(4)
7660(3)
10844(4)
11920(4)
10406(4)
11442(4)
7302(5)
6096(7)
7442(5)
6338(6)
11227(5)
7366(1)
6820(3)
9137(3)
2131(1)
2827(4)
4019(4)
29(1)
43(1)
48(1)
45(1)
37(1)
30(1)
32(1)
34(1)
36(1)
40(1)
73(2)
35(1)
56(1)
34(1)
52(1)
42(1)
35(1)
52(1)
36(1)
48(1)
44(1)
40(1)
55(1)
The yield of complex 4 was 0.043 g (60%).
For C18H28N4O8Cu2 anal. calcd. (%): C, 38.91; H,
5.04; N, 10.08.
5309(3) –244(4)
7453(3)
8284(4)
7579(4)
6910(4)
7946(4)
8018(5)
8080(7)
6197(5) –473(5)
5819(6) –1900(6)
9558(5)
476(3)
1708(4)
1318(4)
3533(4)
4715(4)
3761(5)
4557(7)
Found (%): C, 38.14; H, 4.99; N, 10.14.
IR (KBr),
, cm–1: 3384 m. br, 3238 m. br, 3146 w,
ν
2927 w, 1648 s, 1614 s, 1576 m, 1425 s, 1342 w, 1289 w,
1089 m. br, 786 s, 681 m, 625 m, 467 s. br.
(b) Copper complex
2 (0.1 g, 0.15 mmol) was
added to a solution of 3,5ꢀdimethylpyrazole (0.058 g,
0.6 mmol) in acetonitrile (15 mL), and the mixture
was stirred at 40°С for 1 h. The solution obtained was
concentrated to 7 ml and kept for a day at +5°С. The
1652(5)
2053(6)
1225(5)
1012(5)
532(6)
3560(5)
2413(5)
4750(5)
5473(5)
6835(6)
10311(6) 10654(5)
12561(5)
12961(5)
14252(5)
10592(5)
9611(6)
11733(6)
12251(5)
13419(6)
9669(5)
8385(5)
7828(6)
5652(5)
4262(5)
5886(5)
7357(5)
8275(6)
blue crystals of complex
complex that formed were separated from the
mother liquor by decantation and isolated mechaniꢀ
cally under a microscope. The yield of complex was
was 0.025 g
3 and the green crystals of
4
3
0.071 g (63.4%). The yield of complex
(22.5%).
4
Synthesis of Cu2(
μ
ꢀOOCMe)4(Hdmpz)2 (4)
×
C6H6
(5). Copper complex
2
(0.1 g, 0.15 mmol) was added
to 3,5ꢀdimethylpyrazole (0.029 g, 0.3 mmol) in benꢀ
zene (15 mL). The reaction mixture was stirred at
40°С for 1 h. The solution obtained was concentrated
to 7 mL and kept for 24 h at +5°С. The blue crystals of
separated from the mother liquor by decantation and
isolated mechanically under a microscope. The yield
of complex
3 was 0.016 g (19.4%). The yield of comꢀ
complex
3
and the green crystals of complex
5
were plex
5
was 0.06 g (71.2%).
C(9A)
C(9C)
C(2E)
C(8A)
C(7A)
C(8C)
C(7C)
C(4E)
O(4E)
C(1E)
O(1E)
C(14A)
C(13A)
C(12A)
C(14C)
H(4AC)
N(2A)
H(2AA)
N(1A)
C(3E)
C(5A)
C(6A)
C(10A)
O(3E)
N(2C)
C(13C)
C(5C)
C(12C)
H(2AC)
O(2E)
H(4AA)
N(4A)
Cu(1E)
N(3E)
N(4E)
O(2A) H(4AE)
C(11E)
N(1C)
C(10C)
N(4C)
C(6C)
N(3A)
Cu(1A)
C(11A)
N(3C)
Cu(1C)
C(10E)
N(1E)
C(11C)
O(4C)
O(4A)
C(6E)
C(12E)
C(5E)
H(2AE)
N(2E)
O(2C)
O(3A)
C(13E)
C(3A)
O(3C)
C(1A)
O(1A)
C(14E)
C(3C)
C(4C)
C(7E)
C(4A)
O(1C)
C(8E)
C(1C)
C(2A)
C(9E)
C(2C)
Fig. 3. Intermolecular hydrogen bonding in the crystal of complex
3 leading to the formation of the linear polymer.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 5 2010

720
PEROVA et al.
Table 7. Selected bond lengths (d) and bond angles (ω) for complex 3
Bond , Å
Cu(1)–O(1)
d
Bond
Cu(1)–O(3)
d, Å
2.001(3)
1.998(3)
1.325(5)
1.340(6)
1.365(5)
1.986(3)
1.978(4)
1.363(5)
1.335(5)
1.345(6)
Cu(1)–N(1)
N(1)–C(5)
N(2)–C(8)
N(3)–N(4)
Cu(1)–N(3)
N(1)–N(2)
N(3)–C(10)
N(4)–C(13)
Angle
ω, deg
Angle
ω, deg
N(3)Cu(1)O(3)
O(3)Cu(1)N(1)
O(3)Cu(1)O(1)
C(1)O(1)Cu(1)
N(2)N(1)Cu(1)
N(4)N(3)Cu(1)
169.37(13)
91.48(14)
90.22(14)
101.3(3)
122.4(3)
122.9(3)
N(3)Cu(1)N(1)
N(3)Cu(1)O(1)
N(1)Cu(1)O(1)
C(3)O(4)Cu(1)
C(10)N(3)Cu(1)
89.63(15)
90.66(15)
169.21(13)
102.1(3)
131.5(3)
For C24H34N4O8Cu2 anal. calcd. (%): C, 45.49; H,
5.41; N, 8.84.
IR (KBr),
ν
, cm–1: 3384 m. br, 3238 m. br, 3146 w,
2927 w, 1648 s, 1614 s, 1576 m, 1425 s, 1342 w, 1289 w,
1089 m. br, 786 s, 681 m, 625 m, 467 s. br.
Found (%): C, 44.90; H, 5.21; N, 8.87.
C(7)
C(9)
C(5)
C(6)
C(8)
C(16A)
C(15A)
C(14A)
C(18A)
C(17A)
C(11)
N(2)
N(1)
O(6A)
O(8A)
N(4A)
H(4AA)
O(1)
C(2)
N(3A)
H(2A)
C(10)
O(7A)
Cu(2A)
C(1)
Cu(1)
O(3)
C(4)
C(13A)
C(12A)
O(8)
O(5A)
O(4)
O(2)
C(4A)
O(5)
C(3)
O(2A)
O(4A)
C(3A)
C(12)
C(13)
O(3A)
C(1A)
Cu(1A)
Cu(2)
N(3)
O(7)
C(10A)
H(4A)
H(2AA)
N(1A)
N(4)
O(1A)
O(6)
C(2A)
N(2A)
C(11A)
C(17)
C(8A)
C(5A)
C(14)
C(16)
C(18)
C(15)
C(9A)
C(6A)
C(7A)
Fig. 4. Intermolecular hydrogen bonding in complex
4.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 5 2010

REACTIONS OF AQUEOUS COPPER ACETATE
721
Table 8. Coordinates of atoms (×104) and equivalent isotropic factors (×103, Å2) for complex 4
Atom
x
y
z
Ueq
Atom
x
y
z
Ueq
Cu(1)
Cu(2)
Cu(3)
Cu(4)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
O(10)
O(11)
O(12)
O(13)
O(14)
O(15)
O(16)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
N(7)
N(8)
C(1)
216(1)
209(1) 2123(1)
–839(1) 3002(1)
34(1)
34(1)
38(1)
37(1)
49(1)
46(1)
50(1)
53(1)
43(1)
48(1)
48(1)
52(1)
51(1)
49(1)
53(1)
57(1)
53(1)
53(1)
50(1)
52(1)
39(1)
48(1)
40(1)
40(1)
43(1)
43(1)
44(1)
40(1)
38(1)
58(1)
48(1)
84(1)
C(5)
3434(4)
5045(4)
581(2) 2373(1)
1013(2) 2210(2)
37(1)
56(1)
44(1)
79(1)
46(1)
76(1)
66(1)
64(1)
116(2)
47(1)
80(1)
57(1)
49(1)
71(1)
42(1)
60(1)
46(1)
68(1)
45(1)
64(1)
42(1)
59(1)
50(1)
71(1)
64(1)
54(1)
84(1)
63(1)
113(2)
69(1)
50(1)
69(1)
1494(1)
C(6)
253(1) –4777(1) 2947(1)
1480(1) –5815(1) 1933(1)
C(7)
2406(4) –1553(2) 1782(2)
3351(5) –2236(3) 1300(2)
C(8)
–1583(3)
–644(2) 2350(1)
C(9)
–1426(4)
–1423(6)
–2043(5)
–1833(5)
–2265(7)
660(2)
–406(3)
1443(3)
2267(3)
3336(3)
918(1)
817(2)
585(2)
871(2)
741(3)
–530(3) –1512(2) 3079(1)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
–877(3)
183(3)
1111(2) 2778(1)
236(2) 3508(1)
854(2) 2072(1)
–33(2) 2797(1)
–830(2) 1603(1)
2291(2)
3332(3)
1517(3)
3086(4) –1553(2) 4198(2)
2904(6) –540(3) 4435(2)
2568(3) –1730(2) 2323(1)
1402(3) –5913(2) 3322(1)
2360(3) –6805(2) 2494(1)
–626(3) –3790(2) 2392(1)
362(3) –4669(2) 1559(1)
–1664(3) –5525(2) 2921(1)
–639(3) –6409(2) 2094(1)
2393(3) –4202(2) 2773(1)
3405(3) –5092(2) 1948(1)
3796(5) –2417(3) 4435(2)
3696(4) –3141(2) 4047(2)
4269(5) –4213(2) 4036(2)
2134(4) –6676(2) 3054(2)
2761(5) –7483(2) 3456(2)
–394(4) –3921(2) 1829(2)
–1042(5) –3090(3) 1440(2)
–1765(4) –6146(2) 2536(2)
–3353(4) –6614(3) 2591(2)
3529(4) –4477(2) 2339(2)
5135(4) –4048(3) 2287(2)
–1455(4) –4462(2) 4341(2)
–1620(5) –5535(3) 4418(2)
–1887(5) –3723(3) 4766(2)
–1539(4) –2871(3) 4475(2)
–1719(6) –1830(3) 4680(2)
–867(3)
986(2) 1396(1)
1974(2) 1356(1)
–1131(3)
2579(3) –1732(2) 3679(1)
2965(3) –2709(2) 3596(1)
–845(3) –4086(2) 3806(1)
–916(3) –3115(2) 3900(1)
2438(3) –6654(2) 1122(1)
2724(3) –7641(2) 1167(1)
–1670(4) –1269(2) 2766(2)
–3230(4) –1757(2) 2911(2)
2763(5) –6463(3)
2609(7) –5432(3)
3233(5) –7333(3)
3199(4) –8067(3)
3567(5) –9158(3)
530(2)
295(2)
211(2)
624(2)
563(2)
C(2)
C(3)
–707(4)
944(2) 3317(2)
1666(3) 3789(2)
C(4)
–1656(5)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 5 2010

722
PEROVA et al.
Table 9. Selected bond lengths (d) and bond angles (ω) for complex 4
Bond , Å
Cu(1)–Cu(2)
d
Bond
Cu(3)–Cu(4)
d, Å
2.6788(5)
1.980(2)
1.991(2)
2.171(2)
1.983(2)
1.994(2)
1.968(2)
1.981(2)
2.169(3)
1.979(2)
1.962(2)
2.6889(6)
1.970(2)
1.962(2)
1.971(2)
1.957(2)
2.158(2)
1.967(2)
1.982(2)
1.978(2)
1.965(2)
2.155(3)
Cu(1)–O(1)
Cu(1)–O(5)
Cu(1)–N(1)
Cu(2)–O(4)
Cu(2)–O(8)
Cu(3)–O(9)
Cu(3)–O(13)
Cu(3)–N(5)
Cu(4)–O(14)
Cu(4)–O(16)
Cu(1)–O(3)
Cu(1)–O(7)
Cu(2)–O(2)
Cu(2)–O(6)
Cu(2)–N(3)
Cu(3)–O(11)
Cu(3)–O(15)
Cu(4)–O(10)
Cu(4)–O(12)
Cu(4)–N(7)
Angle
ω, deg
Angle
ω, deg
O(7)Cu(1)O(3)
O(3)Cu(1)O(1)
O(3)Cu(1)O(5)
O(7)Cu(1)N(1)
O(1)Cu(1)N(1)
O(7)Cu(1)Cu(2)
O(1)Cu(1)Cu(2)
N(1)Cu(1)Cu(2)
O(6)Cu(2)O(4)
O(6)Cu(2)O(8)
O(4)Cu(2)O(8)
O(2)Cu(2)N(3)
O(8)Cu(2)N(3)
O(2)Cu(2)Cu(1)
O(8)Cu(2)Cu(1)
O(11)Cu(3)O(9)
O(9)Cu(3)O(13)
O(9)Cu(3)O(15)
O(11)Cu(3)N(5)
O(13)Cu(3)N(5)
O(11)Cu(3)Cu(4)
O(13)Cu(3)Cu(4)
N(5)Cu(3)Cu(4)
O(16)Cu(4)O(10)
O(16)Cu(4)O(14)
O(10)Cu(4)O(14)
O(12)Cu(4)N(7)
O(14)Cu(4)N(7)
O(12)Cu(4)Cu(3)
O(14)Cu(4)Cu(3)
C(1)O(1)Cu(1)
C(3)O(3)Cu(1)
C(5)O(5)Cu(1)
C(7)O(7)Cu(1)
C(19)O(9)Cu(3)
C(21)O(11)Cu(3)
C(23)O(13)Cu(3)
C(25)O(15)Cu(3)
168.28(9)
88.98(9)
89.94(9)
95.52(9)
95.85(9)
82.61(6)
81.72(6)
176.91(7)
90.26(10)
88.46(9)
165.29(9)
95.06(9)
93.22(9)
84.90(6)
84.13(7)
166.43(10)
90.08(10)
88.72(9)
98.74(10)
93.53(10)
85.33(7)
81.64(7)
173.71(7)
89.61(9)
167.43(10)
87.75(9)
98.91(10)
94.55(10)
81.09(7)
84.82(7)
126.42(19)
121.2(2)
123.85(19)
125.7(2)
126.5(2)
121.4(2)
126.4(2)
123.3(2)
O(7)Cu(1)O(1)
O(7)Cu(1)O(5)
O(1)Cu(1)O(5)
O(3)Cu(1)N(1)
O(5)Cu(1)N(1)
O(3)Cu(1)Cu(2)
O(5)Cu(1)Cu(2)
O(6)Cu(2)O(2)
O(2)Cu(2)O(4)
O(2)Cu(2)O(8)
O(6)Cu(2)N(3)
O(4)Cu(2)N(3)
O(6)Cu(2)Cu(1)
O(4)Cu(2)Cu(1)
N(3)Cu(2)Cu(1)
O(11)Cu(3)O(13)
O(11)Cu(3)O(15)
O(13)Cu(3)O(15)
O(9)Cu(3)N(5)
O(15)Cu(3)N(5)
O(9)Cu(3)Cu(4)
O(15)Cu(3)Cu(4)
O(16)Cu(4)O(12)
O(12)Cu(4)O(10)
O(12)Cu(4)O(14)
O(16)Cu(4)N(7)
O(10)Cu(4)N(7)
O(16)Cu(4)Cu(3)
O(10)Cu(4)Cu(3)
N(7)Cu(4)Cu(3)
C(1)O(2)Cu(2)
C(3)O(4)Cu(2)
C(5)O(6)Cu(2)
C(7)O(8)Cu(2)
C(19)O(10)Cu(4)
C(21)O(12)Cu(4)
C(23)O(14)Cu(4)
C(25)O(16)Cu(4)
90.17(9)
87.72(9)
164.32(9)
96.19(9)
99.81(9)
85.70(7)
82.61(6)
168.92(9)
88.57(9)
89.87(9)
95.97(9)
101.49(9)
84.04(6)
81.16(7)
177.35(7)
89.85(9)
87.90(9)
165.29(10)
94.81(9)
101.18(9)
81.24(7)
83.68(7)
89.64(10)
166.15(10)
89.99(10)
97.93(10)
94.89(10)
82.71(7)
85.10(7)
179.37(7)
122.54(19)
125.7(2)
124.12(19)
122.5(2)
121.8(2)
126.5(2)
122.1(2)
125.8(2)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 5 2010

REACTIONS OF AQUEOUS COPPER ACETATE
723
RESULTS AND DISCUSSION
room temperature and the reaction of complex
1
with
a triethylamine excess in acetonitrile in the presence of
We found that the dissolution of aqueous copper
acetate in THF on heating gave dark blue crystals
acetic
acid
yielded
{[Cu2(µꢀOOCMe)4[µꢀ
Cu2(µꢀOOCMe)4(thf)2 (1) that were very unstable at OOCMe(HNEt3)]}n polymer (2):
Cu(OOCMe) · 2H O
2
2
THF,
HOOCMe,
Et3M,
65°C
MeCN
Me
Me
C
Me
C
Me
Me
C
Me
C
C
C
NEt3
H
O
O
O
O
O
O
O
O
O
O
O
O
Cu
O
Cu
O
Cu
Cu
O
Cu
O
Cu
C
Me
O
O
O
O
O
O
C
O
O
O
O
O
O
C
Me
C
Me
C
C
C
Me
n
Me
Me
Me
1
2
4Hdmpz,
22°C
Me
C
Me
C
O
Me
C
Me
C
O
O
H
O
O
O
O
N
O
H
H
N
Cu
Cu
N
Cu
+
N
N
N
N
N
O
O
O
O
H
C
Me
C
Me
3
4
According to the Xꢀray diffraction data, dimer
(Fig. 1, Tables 2, 3) having lantern geometry contains (Fig. 2; Tables 4, 5) in which two dimeric lanterns with
two copper atoms at a distance of 2.587(1) Å linked by close metal–metal distances Сu(1)···Cu(1A)
four acetate bridges (Cu–O 1.953(4)–1.967(4) Å). 2.6339(5) , Cu(2)···Cu(2A) 2.6366(5) Å) and similar
The tetragonal pyramidal environment of each copper geometries of the M2( ꢀOOCMe)4 fragments (Cu(1)–O
1
(HNEt3)+ results in the formation of linear polymer
2
(
Å
µ
atom is supplemented by a coordinated THF molecule 1.967(1) Å, Cu(2)–O 1.962(1)–1.983(1) Å) in the
(Cu–O 2.214(3) Å). Comparison of the geometry of axial position have different donating oxygen atoms:
synthesized complex
1
with that of the characterized hydrogenꢀbonded to the Et3NH+ cation (Cu(1)–O(5)
adducts Cu2(OOCR)2(thf)2 (R = But [2], Ph [15]) 2.125(1) Å) and free (Cu(2)–O(6) 2.112(1) Å). Such
shows that the metal–metal distance increases from an unusual bridging coordination of the [OC(Me)O]–
2.575(2) to 2.607 Å and the Cu–Othf bond length (HNEt3)+ adduct that “crossꢀlinks” two dimeric lanꢀ
decreases simultaneously from 2.226(6) to 2.182
Å
terns is observed for the first time.
The reactions of complexes and
excess yield the blue mononuclear complex
Cu(Hdmpz)2(OOCMe)2 and green Cu2(
OOCMe)4(Hdmpz)2 (
According to the Xꢀray diffraction data, in monoꢀ
nuclear complex the copper atom exists in the plaꢀ
narꢀsquare environment of two oxygen atoms belongꢀ
with a change in the donating ability of substituent R
in the carboxylate anion. These changes in the bond
lengths correspond to the change in the strength of the
carboxylic acids forming the respective anion [16].
According to the Cambridge Crystallographic Data
1
2 with an Hdmpz
(3)
µ
ꢀ
4).
Centre, complex
high value [17].
1 was characterized earlier with a
3
R
According to the Xꢀray diffraction data, the ing to the acetate anions (Cu–O(1),O(3) 1.986(3),
replacement of the coordinated THF molecule in 2.001(3) Å) and two nitrogen atoms of the Hdmpz
complex
1
by the bidentate adduct [OC(Me)O]– molecules (Cu–N 1.978(4), 1.998(3) Å). In the unit
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 5 2010

724
PEROVA et al.
Table 10. Coordinates of atoms (×104) and equivalent isotropic
factors (×103, Å2) for complex 5
cell the NH hydrogen atoms of coordinated pyrazole
of one molecule of complex form short hydrogen
3
bonds with the oxygen atom of the acetate anion of
anther molecule of the complex, which results in the
formation of the linear polymer (N···O 2.740(3),
Atom
x
y
z
Ueq
Cu(1)
Cu(2)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
N(1)
N(2)
N(3)
N(4)
C(1)
5348(1)
5896(1)
4002(3)
6544(3)
7267(3)
3286(3)
6613(3)
4871(3)
3875(3)
4936(1) 4089(1)
9088(1) 5767(1)
6419(2) 3428(2)
3452(2) 5070(2)
5650(2) 4123(2)
4223(2) 4379(2)
8761(2) 4584(2)
9706(2) 6689(2)
8388(2) 5884(2)
41(1)
38(1)
56(1)
53(1)
52(1)
54(1)
56(1)
55(1)
46(1)
48(1)
45(1)
44(1)
43(1)
49(1)
46(1)
67(1)
52(1)
65(1)
54(1)
94(2)
59(1)
54(1)
75(1)
53(1)
92(2)
41(1)
61(1)
49(1)
80(1)
62(1)
59(1)
2.750(3)
that observed in Cu(
Å
; H–O 1.90, 1.95 Å) (Fig. 3) analogous to
µ
ꢀOOCBut)2(Hdmpz)2 [2]. A
molecule of the complex contains weak contacts of the
O(2) and O(4) oxygen atoms with the central copper
atom (Cu···O 2.471(3), 2.487(3) Å).
According to the Xꢀray diffraction data, binuclear
complex 4 (Tables 8, 9) has a traditional lantern geomꢀ
etry with the axially coordinated pyrazole molecules
(in two independent molecules: Cu···Cu 2.6788(5),
2.6889(6)
Å; Сu–O 1.962(2)–1.994(2) Å; Cu–N
2.158(2)–2.171(2) Å). However, unlike the intramoꢀ
lecular hydrogen bonds of the NH fragments of pyraꢀ
zole and the oxygen atom of the bridging anions found
7601(3) 10096(2) 5384(2)
in copper pivalate Cu2(
µ
ꢀOOCBut)4(Hdmpz)2 (the
angle Cu(
µ
ꢀOOBut)/Hdmpz 0о) [2]), in complex
4
5933(3)
6110(3)
7360(3)
7641(3)
3399(4)
2517(5)
7597(4)
9146(4)
6140(4)
6077(6)
6431(5)
6398(4)
6641(5)
6134(5)
6810(6)
2551(4)
1069(4)
8175(4)
8225(5)
8984(5)
8601(5)
9092(6)
4863(2) 2614(2)
3882(2) 2574(2)
7626(2) 7017(2)
6625(2) 7009(2)
6924(3) 3927(3)
8096(3) 3259(3)
5916(3) 4816(3)
6412(3) 4730(3)
5627(3) 1602(3)
6846(3) 1311(3)
intermolecular hydrogen bonds are formed (N···O
2.815(2), 2.918(2) Å; H···O 2.04–2.09 Å), changing
µ
the Cu(
ꢀOOMe)/Hdmpz angle (36.8o, 41.8o in two
independent molecules (Fig. 4). The character of
intermolecular hydrogen bonding and the geometry of
complex
tallization from benzene in complex
(in two independent molecules Cu···Cu 2.6775(8),
2.6881(8) ; Cu–O 1.966(2)–1.984(2) , Cu–N
, N···O 2.818(2), 2.866(2)
angle Cu( ꢀOOMe)/Hdmpz
4
remain almost unchanged upon its recrysꢀ
4
×
0.5 С6Н6 (
5)
C(2)
Å
Å
C(3)
2.160(3), 2.169(3)
H···O 1.98–2.03
Å
Å;
C(4)
Å
,
µ
34.5о, 35.2о) (Tables 10, 11).
C(5)
No analogous intermolecular hydrogen bonds were
observed in the dimer Cu2( ꢀOOCPh)4(Hdmpz)2
Cu···Cu 2.690 , Cu–O 1.965–1.998 , Cu–N
C(6)
µ
C(7)
5129(3)
945(3)
(
Å
Å
2.148 Å), which is due, most likely, to steric effects.
However, this dimer contains no contacts with the
adjacent oxygen atoms of the benzoate anions [18].
C(8)
4011(3) 1584(3)
3035(3) 1351(3)
9408(4) 3633(3)
9121(4) 2767(3)
8916(3) 5359(3)
8317(3) 5651(3)
7457(3) 7885(3)
8392(3) 8165(3)
6368(3) 8414(3)
5852(3) 7845(3)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(1S)
In summary, our studies show that the structures of
the reaction products of copper carboxylates with triꢀ
ethylamine and pyrazole are dictated by the Lewis
acidity of the metal center depending on the donor
ability of substituent R in the carboxylate anion. The
coordination of the [OC(Me)O]–(HNEt3)+ adduct is
observed for less basic acetate anions in the copper
complex, whereas the Cu2(
ꢀOOCBut)4(NEt3)2 comꢀ
µ
plex was obtained for pivalate. No pyrazole deprotoꢀ
nation occurs due to their reactions with 3,5ꢀdimethꢀ
ylpyrazole, and the monoꢀ and binuclear complexes
were isolated, as in the case of pivalates. However,
intermolecular hydrogen bonds are formed in the
binuclear complexes with the bridging acetate anions,
whereas intramolecular hydrogen bonds of the NH
fragments of coordinated pyrazole and the oxygen
atoms of the corresponding anion are formed in the
complex with the pivalate anion.
4681(3) 7998(4) 107(2)
8810(30) 9476(16) 228(11) 222(8)
C(2S) 10240(40) 8750(11) 472(13) 289(11)
C(3S) 8500(20) 10530(20) –163(10) 271(8)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 5 2010

REACTIONS OF AQUEOUS COPPER ACETATE
725
Table 11. Selected bond lengths (d) and bond angles (ω) for complex 5
Bond , Å
Cu(1)–O(3)
d
Bond
Cu(1)–O(1)
d, Å
1.970(2)
1.971(2)
2.160(3)
1.967(2)
1.973(2)
2.169(3)
1.966(2)
1.996(2)
2.6881(8)
1.971(2)
1.984(2)
2.6775(8)
Cu(1)–O(2)
Cu(1)–N(1)
Cu(2)–O(6)
Cu(2)–O(8)
Cu(2)–N(3)
Cu(1)–O(4)
Cu(1)–Cu(1)#1
Cu(2)–O(5)
Cu(2)–O(7)
Cu(2)–Cu(2)#2
Angle
ω, deg
Angle
ω, deg
O(3)Cu(1)O(1)
O(1)Cu(1)O(2)
O(1)Cu(1)O(4)
O(3)Cu(1)N(1)
O(2)Cu(1)N(1)
O(3)Cu(1)Cu(1)#1
O(2)Cu(1)Cu(1)#1
N(1)Cu(1)Cu(1)#1
O(6)Cu(2)O(8)
O(6)Cu(2)O(7)
O(8)Cu(2)O(7)
O(5)Cu(2)N(3)
O(7)Cu(2)N(3)
O(5)Cu(2)Cu(2)#2
O(7)Cu(2)Cu(2)#2
C(1)O(1)Cu(1)
C(3)O(3)Cu(1)
C(10)O(5)Cu(2)
C(12)O(7)Cu(2)
89.48(10)
166.53(9)
89.12(10)
96.41(10)
96.28(10)
82.60(7)
84.27(7)
178.87(8)
90.08(10)
88.25(10)
166.65(9)
95.38(10)
97.30(10)
85.14(8)
83.30(7)
125.0(2)
126.4(2)
121.5(2)
123.9(2)
O(3)Cu(1)O(2)
89.93(10)
166.53(9)
88.32(10)
97.16(10)
97.07(10)
82.31(7)
83.93(7)
167.05(9)
88.96(10)
89.70(10)
97.56(10)
96.05(10)
81.93(7)
83.35(7)
179.20(8)
122.2(2)
122.6(2)
125.2(2)
124.6(2)
O(3)Cu(1)O(4)
O(2)Cu(1)O(4)
O(1)Cu(1)N(1)
O(4)Cu(1)N(1)
O(1)Cu(1)Cu(1)#1
O(4)Cu(1)Cu(1)#1
O(6)Cu(2)O(5)
O(5)Cu(2)O(8)
O(5)Cu(2)O(7)
O(6)Cu(2)N(3)
O(8)Cu(2)N(3)
O(6)Cu(2)Cu(2)#2
O(8)Cu(2)Cu(2)#2
N(3)Cu(2)Cu(2)#2
C(1)#1O(2)Cu(1)
C(3)#1O(4)Cu(1)
C(10)#2O(6)Cu(2)
C(12)#2O(8)Cu(2)
Note: Symmetry transformations used for the generation of equivalent atoms: #1 –x + 1, –y + 1, –z + 1; #2 –x + 1, –y + 2, –z + 1.
2. T. O. Denisova, E. V. Amel’chenkova, I. V. Pruss, et al.,
Zh. Neorg. Khim. 51 (7), 1098 (2006) [Russ. J. Inorg.
Chem. 51 (7), 1020 (2006)].
ACKNOWLEDGMENTS
This work was supported by the Russian Foundaꢀ
tion for Basic Research (project nos. 08ꢀ03ꢀ01063 and
08ꢀ03ꢀ90455), the Foundation of the President of the
Russian Federation (Program for Support of the
Leading Scientific Schools of Russia, grant NShꢀ
1764.2003.03), and the Presidium and Division of
Chemistry and Materials Science of the Russian
Academy of Sciences (programs “Theoretical and
Experimental Investigation of the Nature of the
Chemical Bond and Mechanisms of the Most Imporꢀ
tant Chemical Reactions and Processes” and “Target
Synthesis of Inorganic Substances and Creation of
Functional Materials”).
3. T. O. Denisova, Zh. V. Dobrokhotova, V. N. Ikorskii,
and S. E. Nefedov, Zh. Neorg. Khim. 51 (9), 1363
(2006) [Russ. J. Inorg. Chem. 51 (9), 1363 (2006)].
4. E. V. Amel’chenkova, T. O. Denisova, and S. E. Nefeꢀ
dov, Zh. Neorg. Khim. 51 (8), 1304 (2006) [Russ.
J. Inorg. Chem. 51 (8), 1218 (2006)].
5. T. O. Denisova, G. G. Aleksandrov, O. P. Fialkovskii,
and S. E. Nefedov, Zh. Neorg. Khim. 48 (9), 1476
(2003) [Russ. J. Inorg. Chem. 48 (9), 1340 (2003)].
6. E. V. Amel’chenkova, T. O. Denisova, and S. E. Nefeꢀ
dov, Zh. Neorg. Khim. 51 (11), 1763 (2006) [Russ.
J. Inorg. Chem. 51 (11), 1763 (2006)].
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RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 5 2010