Synthesis and crystal structure of dimethylgold(III) carboxylates

Article abstract of DOI:10.1134/s1070328408010119

Three novel carboxylate complexes were synthesized: dimethylgold(III) trifluoroacetate [Me₂Au(Tfa)]₂ (I), trimethylacetate (pivalate) [Me₂Au(Piv)]₂ (II), and benzoate [Me ₂Au(OBz)]₂ (III). The starting reagent was [Me ₂AuI]₂. The procedure of its synthesis provides 60% product yield. Dimethylgold(III) carboxylates were identified from the IR and ¹H NMR data. The title compounds were studied by X-ray diffraction. The unit cell parameters for I, C₈H₁₂Au₂F ₆O₄: a = 15.5522(13), b = 12.9398(11), c = 15.6555(14) ?, β = 104.308(2)°, Z = 8, ρ(calcd.) = 2.959 g/cm ³, space group C2/c, R = 0.0779; for II, C₁₄H ₃₀Au₂O₄: a = 10.3025(3), b = 15.5952(4), c = 12.6819(3) ?, β = 105.8270(10)°, Z = 4, ρ(calcd.) = 2.224 g/cm³, space group P2₁/c, R = 0.0229; for III, C ₁₈H₂₂Au₂O₄: a = 12.8050(2), b = 19.7886(3), c = 7.60300(10) ?, Z = 4, ρ(calcd.) = 2.401 g/cm ³, space group Pnma, R = 0.0144. Compounds I-III have the molecular structures; the structural units are the [(CH₃)₂Au(OOCR)] ₂ dimers (AuAu 2.984-3.080 ?), R = CF₃, tert-Bu, Ph. The gold atoms have the square coordination with two carbon atoms and two oxygen atoms (Au-O 2.120-2.173 ?). The molecules in compounds I-III are united into infinite unidimensional chains connected by van der Waals interactions.

Full text of DOI:10.1134/s1070328408010119

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2008, Vol. 34, No. 1, pp. 70–77. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © A.A. Bessonov, N.B. Morozova, N.V. Kurat’eva, I.A. Baidina, N.V. Gel’fond, I.K. Igumenov, 2008, published in Koordinatsionnaya Khimiya, 2008,
Vol. 34, No. 1, pp. 73–80.
Synthesis and Crystal Structure
of Dimethylgold(III) Carboxylates
A. A. Bessonov, N. B. Morozova, N. V. Kurat’eva, I. A. Baidina, N. V. Gel’fond, and I. K. Igumenov
Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 3, Novosibirsk, 630090 Russia
E-mail: bessonov@che.nsk.su
Received February 20, 2007
Abstract—Three novel carboxylate complexes were synthesized: dimethylgold(III) trifluoroacetate
[Me2Au(Tfa)]2 (I), trimethylacetate (pivalate) [Me2Au(Piv)]2 (II), and benzoate [Me2Au(OBz)]2 (III). The
starting reagent was [Me2AuI]2. The procedure of its synthesis provides 60% product yield. Dimethylgold(III)
carboxylates were identified from the IR and 1H NMR data. The title compounds were studied by X-ray dif-
fraction. The unit cell parameters for I, C8H12Au2F6O4: a = 15.5522(13), b = 12.9398(11), c = 15.6555(14) Å,
β = 104.308(2)°, Z = 8, ρ(calcd.) = 2.959 g/cm3, space group C2/c, R = 0.0779; for II, C14H30Au2O4: a =
10.3025(3), b = 15.5952(4), c = 12.6819(3) Å, β = 105.8270(10)°, Z = 4, ρ(calcd.) = 2.224 g/cm3, space group
P21/c, R = 0.0229; for III, C18H22Au2O4: a = 12.8050(2), b = 19.7886(3), c = 7.60300(10) Å, Z = 4,
ρ(calcd.) = 2.401 g/cm3, space group ênma, R = 0.0144. Compounds I–III have the molecular structures; the
structural units are the [(CH3)2Au(OOCR)]2 dimers (Au···Au 2.984–3.080 Å), R = CF3, tert-Bu, Ph. The gold
atoms have the square coordination with two carbon atoms and two oxygen atoms (Au−O 2.120–2.173 Å). The
molecules in compounds I−III are united into infinite unidimensional chains connected by van der Waals inter-
actions.
DOI: 10.1134/S1070328408010119
The gold complexes with the organic ligands are diethyl ether cooled to –30°ë. The reaction was per-
used in plating of the functional gold-containing coat- formed in the flow of argon. The reaction mixture was
ings and films by the chemical vapor deposition method
[1, 2]. The data on the synthesis procedures and struc-
tures of the organic complexes of gold will simplify the
choice of compounds for their practical use.
slowly heated to –10°ë for 30 min and treated with gla-
cial water acidified with HCl. The organic fraction was
separated, an aqueous fraction was extracted with the
large quantity of hexane. After the solvents had been
distilled off, the product was purified by recrystalliza-
tion from hexane. The product yield 0.56 g (60%).
Previously, we studied the crystal chemical and
thermal properties of dimethylgold(III) acetate,
[Me2Au(OAc)]2 (IV) [3]. This work continues our
investigations of a series of dimethylgold(III) carboxy-
lates and describes the synthesis and X-ray diffraction
data on the crystal structure of dimethylgold(III) triflu-
oroacetate [Me2Au(Tfa)]2 (I), pivalate [Me2Au(Piv)]2
(II), and benzoate [Me2Au(OBz)]2 (III). The above
compounds have been synthesized for the first time.
Synthesis of [Me2AuOOCR]2 (R = CF3 (I), tert-Bu
(II), Ph (III)). The equimolar amount of [Me2AuI]2 dis-
solved in toluene was added with stirring to a mixture
of RCOOAg in toluene. The reaction was performed at
room temperature for 1 h in continuous argon flow. The
reaction mixture was filtered to separate the precipitate
formed, and the solvent was evaporated without heat-
ing. The product was purified by recrystallization from
hexane at –10°ë.
EXPERIMENTAL
Compound I forms colorless crystals (mp = 102–
103°ë).
The title compounds were synthesized from the cor-
responding silver carboxylates and dimethylgold(III)
iodide. Silver carboxylates were prepared by the reaction
of Ag2O with RCOOH, where R = CF3, tert-Bu, Ph [4].
The IR spectrum (ν, cm–1): 3007, 2914, 2808, 1677,
1434, 1213, 1134, 838, 805, 725, 517, 479. The
1H NMR spectrum (δ, ppm): 1.37 s (Au–CH3).
Synthesis of [Me2AuI]2. A weighed sample of
KAuCl4 (1.00, 2.65 mmol) that was previously dried in
a vacuum was added with stirring to a solution of MeLi
Compound II forms colorless crystals (mp =
(10.6 mmol) in 70 ml of hexane and 40 ml of absolute 75−76°C).
70

SYNTHESIS AND CRYSTAL STRUCTURE
Table 1. The elemental analysis of dimethylgold carboxylates I–III
71
Content (found/calcd.), %
H
No.
Empirical formula
Yield, %
C
F
I
C8H12Au2F6O4
14.15/14.13
26.45/25.62
32.39/32.54
1.80/1.78
4.58/4.61
3.48/3.34
16.89/16.76
90
94
78
II
III
C14H30Au2O4
C18H22Au2O4
The IR spectrum (ν, cm–1): 2960, 2917, 2869, 1554,
1482, 1414, 1375, 1360, 1231, 1213, 829, 784, 616,
433. The 1H NMR spectrum (δ, ppm): 1.10 s
(Au−CH3), 1.12 Ò. (CH3).
Compound III occurs as white crystals (mp = 185–
187°C) and melts with decomposition.
The IR spectrum (ν, cm–1): 2995, 2915, 2802, 1595,
1552, 1396, 1237, 1221, 1171, 1069, 1026, 834, 714,
688, 596, 473. The 1H NMR spectrum (δ, ppm): 1.28 s
(Au−CH3), 7.32–8.03 m (C6H5).
Complexes I–III are readily soluble in many
organic solvents and are stable at room temperature for
several weeks. The powder X-ray diffraction data for
I−III confirm single-phase nature of the products. The
single crystals for X-ray diffraction were grown by
and summary of data collection are given in Table 2.
The structure was solved by the heavy atom method
and refined in the anisotropic-isotropic (for the H
atoms) approximation; the positions of the hydrogen
atoms were determined geometrically.
The coordinates and the thermal parameters of the
basis atoms are listed in Table 3, the main bond lengths
and the bond angles are presented in Table 4. The cal-
culations were performed with the SHELX-97 program
package [5]. The X-ray diffraction pictures of the com-
pounds under consideration were fully indexed using
the results of the single crystal studies.
RESULTS AND DISCUSSION
It is common practice to use [Me2AuX]2 (X = Cl, Br,
crystallization from hexane. Complexes I, II crystallize I) as the starting reagents in the synthesis of the most
as colorless plates belonging to the monoclinic crystal dimethyl-substituted complexes of gold(III) with the
system. Crystals III belong to the rhombic crystal sys- organic ligands [6, 7]. The main methods of the synthe-
tem. The product yields and the chemical analysis data sis of dimethylgold(II) halides include the interaction
are given in Table 1.
of MeLi with AuX3 [8, 9] or HAuCl4 [10], the reaction
of MeMgX with KAuCl4 [11], AuX3, with pyridine-sub-
stituted halides of gold [12, 13], and the synthesis from
HAuCl4 and SnMe4 [14]. The product yield in the above
methods does not exceed 40–50%.
In this work, we synthesized the novel organic com-
plexes of gold I–III using dimethylgold(III) iodide as
the starting reagent. Previously, [Me2AuI]2 was pre-
pared from AuCl3Py and MeMgI with the yield of 21%
[12] and 35% [15]. The authors of [13] performed the
reaction of the Grignard reagent with [AuCl3(R-Py)]
(R = Alk) and increased the yield of dimethylgold
iodide to 43–45%; the variation of the alkyl radical pro-
duced insignificant effect on the product yield. The best
results have been achieved by the reaction of the Grig-
nard reagent with KAuCl4 (50–55%) [11, 16]. The vari-
The elemental analysis was performed on the Carlo
Erba 1106 analyzer; the error of the C, H determination
was 0.3% and 0.5% for halogen determination.
The IR spectra were recorded on a SPECORD 75IR
instrument at 400−4000 cm–1 (KBr pellets).
The 1H NMR spectra were recorded on a MSL 300
instrument (Bruker) with the CDCl3 solvent and CçCl3
(δH 7.24 ppm) used as the internal standard.
The powder X-ray diffraction analysis of com-
pounds I–III was performed on a DRON-3M diffracto-
meter (CuKα radiation) in the range of angles 2θ =
5°−50° at room temperature.
X-ray diffraction analysis. The unit cell parame-
ters and the experimental intensities for refinement of
crystal structures I–III were measured at 123–150 K on ation of the reaction conditions we performed here did
an automated four-circle Bruker-Nonius X8Apex dif- not increase the product yield [3]. In this paper, we sug-
fractometer equipped with a two-coordinate CCD gested the procedure of the synthesis, where the inter-
detector (MoKα radiation, graphite monochromator). action of methyllithium with KAuCl4 gives dimeth-
The crystallographic parameters of complexes I–III ylgold iodide in 60% yield. The reagents were mixed at
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 34 No. 1 2008

72
BESSONOV et al.
Table 2. The crystallographic parameters and summary of data collection for compounds I–III
Value
Parameter
I
II
III
å
680.11
Monoclinic
C2/c
656.32
Monoclinic
P21/c
696.29
Rhombic
ênma
Crystal system
Space group
a, Å
15.5522(13)
12.9398(11)
15.6555(14)
104.308(2)
3052.8(5)
8
10.3025(3)
15.5952(4)
12.6819(3)
105.8270(10)
1960.35(9)
4
12.8050(2)
19.7886(3)
7.60300(10)
90
b, Å
c, Å
β, deg
V, Å3
1926.55(5)
4
Z
ρ(calcd.), g/cm3
µ, mm–1
F(000)
2.959
2.224
2.401
19.271
14.959
15.229
2432
1216
1280
Range of θ, deg
Range of indices
2.07–32.64
2.05–30.48
2.87–32.58
–16 ≤ h ≤ 23,
–13 ≤ k ≤ 19,
–23 ≤ l ≤ 23
–14 ≤ h ≤ 14,
–22 ≤ k ≤ 22,
–9 ≤ l ≤ 17
–19 ≤ h ≤ 11,
–29 ≤ k ≤ 29,
–11 ≤ l ≤ 9
Number of reflections
12996
5290; 0.0548
3941
18055
5848; 0.0250
4342
19324
3600; 0.0229
3268
Number of independent reflections; Rint
Number of reflections with I > 2σ (I)
Number of refined parameters
GOOF
186
192
156
1.110
1.030
1.029
R for reflections with I >2σ (I)
R1 = 0.0779
wR2 = 0.2329
R1 = 0.0229
wR2 = 0.0527
R1 = 0.0144
wR2 = 0.0309
R for all reflections
R1 = 0.1053
wR2 = 0.2456
R1 = 0.0394
wR2 = 0.0555
R1 = 0.0188
wR2 = 0.0321
Residual electron density (min/max), e/Å3
8.063/–5.614
0.914/–0.700
0.938/–1.122
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SYNTHESIS AND CRYSTAL STRUCTURE
73
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 34 No. 1 2008

74
BESSONOV et al.
Table 4. The main bond lengths and bond angles in compounds I–III*
Bond
d, Å
Bond
d, Å
Bond
d, Å
I
Au(1)–C(2M)
Au(1)–C(1M)
Au(1)–O(4)
Au(1)–O(1)
Au(2)–C(3M)
2.00(3)
Au(2)–C(4M)
Au(2)–O(3)
Au(2)–O(2)
O(1)–C(1)
2.016(18)
2.151(16)
2.165(12)
1.25(2)
C(1)–C(2)
1.52(2)
1.22(3)
1.28(3)
1.54(3)
2.03(2)
O(3)–C(3)
O(4)–C(3)
C(3)–C(4)
2.150(14)
2.173(15)
1.982(17)
O(2)–C(1)
1.25(2)
II
Au(1)–C(2M)
Au(1)–C(1M)
Au(1)–O(3)
Au(1)–O(1)
Au(2)–C(4M)
2.015(5)
2.018(4)
2.120(3)
2.131(3)
2.017(4)
Au(2)–C(3M)
Au(2)–O(4)
Au(2)–O(2)
O(1)–C(1)
2.030(4)
2.126(3)
2.135(3)
1.249(5)
1.242(5)
C(1)–C(2)
O(3)–C(3)
O(4)–C(3)
C(3)–C(4)
1.538(6)
1.246(5)
1.270(5)
1.534(6)
O(2)–C(1)
III
Au(1)–C(1M)
Au(1)–O(1)
Au(2)–C(2M)
Angle
2.021(3)
2.1400(16)
2.017(3)
ω, deg
Au(2)–O(2)
O(1)–C(1)
O(2)–C(1)
Angle
2.1301(16)
1.251(2)
1.251(2)
ω, deg
C(1)–C(2)
1.502(3)
Angle
ω, deg
I
C(2M)Au(1)C(1M)
C(2M)Au(1)O(4)
C(1M)Au(1)O(4)
C(2M)Au(1)O(1)
C(1M)Au(1)O(1)
O(4)Au(1)O(1)
88.2(12)
90.2(10)
176.9(8)
176.8(8)
93.1(10)
88.4(6)
C(4M)Au(2)O(3)
C(3M)Au(2)O(2)
C(4M)Au(2)O(2)
O(3)Au(2)O(2)
C(1)O(1)Au(1)
C(1)O(2)Au(2)
O(2)C(1)O(1)
178.1(7)
175.6(7)
92.9(8)
O(1)C(1)C(2)
C(3)O(3)Au(2)
C(3)O(4)Au(1)
O(3)C(3)O(4)
O(3)C(3)C(4)
O(4)C(3)C(4)
114.3(17)
125.3(13)
126.1(12)
129.5(17)
117(2)
88.2(6)
124.0(12)
126.6(10)
130.1(15)
115.6(15)
113.4(19)
C(3M)Au(2)C(4M)
C(3M)Au(2)O(3)
87.9(9)
90.8(8)
O(2)C(1)C(2)
II
C(2M)Au(1)C(1M)
C(2M)Au(1)O(3)
C(1M)Au(1)O(3)
C(2M)Au(1)O(1)
C(1M)Au(1)O(1)
O(3)Au(1)O(1)
88.3(2)
C(3M)Au(2)O(4)
C(4M)Au(2)O(2)
C(3M)Au(2)O(2)
O(4)Au(2)O(2)
C(1)O(1)Au(1)
C(1)O(2)Au(2)
O(2)C(1)O(1)
177.96(15)
174.24(15)
91.15(17)
90.07(13)
128.3(3)
O(1)C(1)C(2)
C(3)O(3)Au(1)
C(3)O(4)Au(2)
O(3)C(3)O(4)
O(3)C(3)C(4)
O(4)C(3)C(4)
116.0(4)
126.6(3)
127.5(3)
126.0(4)
116.7(4)
117.3(4)
90.88(19)
178.88(19)
172.34(16)
92.06(19)
88.83(15)
87.5(2)
126.1(3)
C(4M)Au(2)C(3M)
C(4M)Au(2)O(4)
125.9(4)
91.09(17)
O(2)C(1)C(2)
118.1(4)
III
C(1M)#Au(1)C(1M)
C(1M)#Au(1)O(1)
C(1M)Au(1)O(1)
O(1)Au(1)O(1)#
87.5(2)
C(2M)#Au(2)C(2M)
C(2M)#Au(2)O(2)
C(2M)Au(2)O(2)
O(2)Au(2)O(2)#
88.4(3)
C(1)O(1)Au(1)
C(1)O(2)Au(2)
O(2)C(1)O(1)
130.18(14)
123.77(14)
126.27(19)
176.35(9)
91.11(13)
90.09(12)
178.81(12)
92.19(15)
87.22(11)
* The symmetry transformations for the equivalent atoms in III: # x, –y + 1/2, z.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 34 No. 1 2008

SYNTHESIS AND CRYSTAL STRUCTURE
75
(a)
(b)
(c)
C(5)
C(7)
F(3)
F(2)
F(4)
C(22)
C(21)
C(4)
C(3)
C(43)
C(42)
C(5A)
C(3A)
F(1)
C(23)
C(1)
C(6)
C(4)
C(3)
O(3)
C(6)
O(2)
C(7A)
C(6A)
C(4)
C(4A)
C(2)
C(1)
C(2)
C(5)
O(1)
F(5)
O(4)
C(3)
C(41)
O(2)
C(2A)
O(1)
O(3)
C(1A)
O(1)
O(4)
O(2)
O(1A)
O(2A)
Au(2)
Au(1)
Au(2)
Au(1)
Au(1)
Au(2)
C(3MB)
C(4MB)
C(1MB)
C(2MB)
C(3M)
C(4M)
C(1ME)
C(1M)
C(2M)
C(1MA)
C(2ME)
C(2MA)
Fig. 1. The structure of the molecule of (a) [Me Au(Tfa)] (I), (b) [Me Au(Piv)] (II), and (c) [Me Au(OBz)] (III) with atomic
2
2
2
2
2
2
numbering.
–30°ë; the lowering of the temperature to –70°ë did not synthesis with 60% yield. The results close to our data
were obtained by the authors of [16].
affect the [Me2AuI]2 yield. The analogous lowering of
the temperature from −23°C to –70°ë performed in
[13] did not change the product yield either; however,
the yield decreased sharply to 15% when the reaction
was run at –10°ë. An increase in the molar amount of
MeLi from 3 to 6 relative to KAuCl4 did not produce
substantial effect on the dimehtylgold(III) iodide yield.
Upon variation of the solvent ratio, the best results were
attained at the 1.75 : 1 ratio of hexane and ether. When
the reaction was performed for more than one hour, the
yield of [Me2AuI]2 decreased. Thus, we suggested and
The synthesis of I–III was based on the method [3],
where complex IV was prepared from silver acetate and
dimethylgold(III) iodide. In the case of dimeth-
ylgold(III) carboxylates, the reaction time was reduced
to 1 h and the flow of argon was passed through the
reaction mixture. The procedure of the synthesis we
developed makes it possible to obtain dimethylgold(III)
carboxylates in high yields (Table 1).
The IR spectra of compounds I–III contain charac-
teristic stretching vibrations ν(C–H)(Au–CH3) in a
range of 2800−3000 cm–1. The analogous vibrations are
optimized the procedure of the dimethylgold(III) iodide observed for dimethylgold(III) acetate at 2850–
Table 5. The crystallographic characteristics and average geometric parameters of dimethylgold(III) carboxylates I–IV
d, Å
ρ(calcd.),
Complex Tmp, °C Crystal system
V/Z, Å3
g/cm3
Au···Au
between
the dimmers
Au···Au
in the dimer
Au–O
Au–C(Me)
IV*
I
95–96 Monoclinic
102–103 Monoclinic
75–76 Monoclinic
185–187 Rhombic
2.917
2.959
2.224
2.401
325.70
381.60
490.09
481.64
2.989
3.080
3.028
2.984
3.637
3.294; 3.462
3.479
2.125
2.160
2.128
2.135
2.023
2.007
2.020
2.019
II
III
3.468
* The data of [3].
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 34 No. 1 2008

76
BESSONOV et al.
observed in a lower field (1.37 ppm) as compared to the
(a)
other carboxylates. The value δç(Au–CH3) in the
1H NMR spectrum of complex II (1.10 ppm) is close to
that of the analogous shift for IV (1.13 ppm) [3].
Au(2A)
Au(1B)
3.294
Au(2)
3.080
Au(1A)
Au(2B)
The molecular structure of the complexes under
consideration consists of neutral binuclear molecules of
[(ëç3)2Au(OOCR)]2 (R = CF3 (I), C(CH3)3 (II), and
C6H5 (III)), whose structures are shown in Fig. 1. Some
characteristics of the novel complexes I–III are com-
pared with similar characteristics of the previously
studied complex IV [3] in Table 5. The square coordi-
nation of the Au atom in I–IV involves two C atoms of
the methyl groups and two O atoms of two carboxylate
groups. The difference between the average Au–Cç3
and Au–O distances for complexes I–IV does not
exceed 0.016 and 0.035 Å, respectively. The bond
angles at the Au atoms deviate from 90° by no more
than 3.1°. The coordination squares of Au(1) and Au(2)
in the dimers are not parallel, and the angles between
the normals to their planes are 34.5°, 36.9°, and 31.8°
for compounds I, II, III, respectively. In the binuclear
molecules, the bridging carboxylate groups form two
five-membered chelate rings with the angle between the
normals to their plane being on the average ~90.8°. The
lengths of the analogous bonds O–C and ë–ëMe in the
carboxylate groups of compounds I–III are almost
equal, their average values being 1.25 and 1.52 Å,
respectively. The average bond lengths in the substitu-
ents are: C–F 1.30 Å in I, C–C 1.533 Å in II and
1.389 Å in III. The planes of the phenyl radicals in
complex III make an angle of 9.4° with the planes of
the metal rings.
3.462
Au(1)
(b)
Au(2B)
Au(1A)
3.479
Au(2)
Au(2A)
3.479
3.028
Au(1B)
Au(1)
(c)
Au(1)
2.986
3.468
Au(2A)
Au(1A)
Au(2)
3.468
Au(1B)
Au(2B)
In the structures of compounds I–III, the dimeric
molecules are packed into infinite unidimensional
chains (Fig. 2). The Au···Au distances between the mol-
ecules in the chains of II and III are equal (~3.47 Å),
while in compound I, this distance is somewhat shorter
and is equal to 3.29 Å. Thus, the coordination of gold is
completed to the square bipyramid with the second Au
atom in the dimer and with the H(Me) atoms of the
neighboring complexes (Au···ç ~3.3 Å) for com-
pounds II and III and with the Au atom of the neigh-
boring molecule of the chain in complex I. In all the
three compounds, the molecules form zigzag chains,
the average AuAuAu angles being ~156° in I, 162° in
II, and 173° in III.
Fig. 2. The fragment of the chain of the molecules in the
crystal of (a) I, (b) II, and (c) III.
2960 cm–1 [3]. The bending vibrations of the Au–CH3
bond are observed in the region 1210–1240 cm–1 (for
IV, 1216–1235 cm–1 [3]). The bending vibrations of the
phenyl substituents C–C–C in complex III and the
stretching vibrations of the C–F bond in complex I
appear in a range of 1000−1200 cm–1. The intense
vibrations ν(C–O) typical of all the chelates are
observed in the frequency interval 1360–1700 cm–1. For
dimethylgold acetate IV, the stretching vibrations of the
C–O bond appear at 1420–1580 cm–1 [3]. In the region
400−900 cm–1, the largest contribution is produced by
the vibrations of the bonds Au−O, C−R (R = CF3, tert-
Bu, Ph), the deformation of the chelate ring and the
ligand substituents.
The general packing of complexes in crystals I–III
is shown in Fig. 3. The dimeric chains are linked by the
van der Waals interactions, the shortest distances H···H
and F···F being 2.3 and 2.8 Å, respectively. The Au···Au
distances between the chains exceed 7.2 Å.
1
The H NMR spectra of compounds I–III contain
ACKNOWLEDGMENTS
typical singlet signal due the protons of the methyl
group δç(Au–CH3) in the region 1.1−1.4 ppm. In the
spectrum of compound I, the singlet δç(Au–CH3) is
The authors are grateful to A. V. Alekseev for per-
forming the powder X-ray diffraction experiment and
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 34 No. 1 2008

SYNTHESIS AND CRYSTAL STRUCTURE
77
(c)
(a)
(b)
y
y
x
z
0
z
0
x
0
Fig. 3. The molecular packing in the crystal of (a) I, (b) II, and (c) III.
16), Clark, R.J.H., Ed., Amsterdam: Elsever Science Ltd,
toA. I. Smolentsev for performing the X-ray diffraction
analysis. This work was supported by NPF OOO
“TECHNOLET-ZOLOTO” in the framework of the
State Contract no. 3631p/6147 with the Foundation for
assistance to small business in the area of science and
technology.
1978.
7. Anderson, G.K., Adv. Organomet. Chem., 1982, vol. 20,
p. 39.
8. Gilman, H. and Woods, L.A., J. Am. Chem. Soc., 1948,
vol. 70, no. 2, p. 550.
9. Perevalova, E.G., Grandberg, K.I., Lemenovskii, D.A.,
and Baukova, T.V., Izv. Akad. Nauk SSSR, Ser. Khim.,
1971, no. 9, p. 2077.
REFERENCES
10. Shiotani, A. and Schmidbaur, H., Chem. Ber., 1971,
1. The Chemistry of Metal CVD, Kodas T.T. and Hampden-
vol. 104, no. 9, p. 2838.
Smith M.J., Eds., New York: VCH, 1994.
11. Zharkova, G.I., Igumenov, I.K., and Zemskov, S.V.,
2. Semyannikov, P.P., Moroz, B.L., Trubin, S.V., et al., Zh.
Strukt. Khim., 2006, vol. 47, no. 3, p. 473.
Koord. Khim., 1980, vol. 6, no. 5, p. 720.
12. Brain, F.H. and Gibson, C.S., J. Chem. Soc., 1939,
3. Bessonov, A.A., Baidina, I.A., Morozova, N.B., et al.,
p. 762.
Zh. Strukt. Khim., 2007, vol. 48, no. 2, p. 289.
13. Hirot, U., Noriyasu, S., and Katsumi, O., IP 06–107670,
Mitsubishi Materials. Corp. Appl., no. 04-279305, 1994.
14. Paul, M. and Schmidbaur, H., Z. Naturforsch., A: Phys.
Sci., 1994.
4. Brauer, G., Vaigel’, F., Kyuil’, Kh., et al., Handbuch der
preparativen Anorganische Chemie, Brauer, G., Ed.,
Stuttgart, 1981.
5. Sheldrick, G.M., SHELX-97. Release 97-1, Göttingen
15. Miles, M.G., Glass, G.E., and Tobias, R.S., J. Am. Chem.
Soc., 1966, vol. 88, no. 24, p. 5738.
(Germany): Univ. of Göttingen, 1997.
6. Puddephatt, R.J., The Chemistry of Gold (Topics in Inor- 16. Zharkova, G.I., Baidina, I.A., and Igumenov, I.K., Zh.
ganic Chemistry and General Chemistry, Monograph Strukt. Khim., 2007, vol. 48, no. 1, p. 108.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 34 No. 1 2008