Synthesis, properties and crystal structures of volatile dimethylgold(III) complexes based on phenyl-containing β-diketones and β-iminoketone

Article abstract of DOI:10.1016/j.poly.2009.12.026

We have synthesized and studied volatile dimethylgold(III) complexes based on phenyl-containing β-diketones and β-iminoketone, namely (CH₃)₂Au(C₆H₅-CO-CH-CO-CH ₃), (CH₃)₂Au(bac) (1); (CH₃)₂Au(C₆H₅-CO-CH-CO-CF ₃), (CH₃)₂Au(btfa) (2); and (CH₃)₂Au(C₆H₅-CO-CH-C(NH)-CH ₃), (CH₃)₂Au(i-bac) (3). The obtained compounds were identified by elemental analysis, ¹H NMR and IR-spectroscopy, and were characterized by DTA and single-crystal X-ray diffraction studies. In compounds 2 and 3, the Au atom has a square coordination environment AuC₂O₂ and AuC₂NO, respectively.

Full text of DOI:10.1016/j.poly.2009.12.026

Polyhedron 29 (2010) 1049–1054
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Polyhedron
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Synthesis, properties and crystal structures of volatile dimethylgold(III)
complexes based on phenyl-containing b-diketones and b-iminoketone
*
G.I. Zharkova , I.A. Baidina, T.S. Yudanova
Nikolaev Institute of Inorganic Chemistry, Siberian Division of Russian Academy of Sciences, Pr. Lavrentiev 3, Novosibirsk 630090, Russia
a r t i c l e i n f o
a b s t r a c t
Article history:
We have synthesized and studied volatile dimethylgold(III) complexes based on phenyl-containing b-
diketones and b-iminoketone, namely (CH3)2Au(C6H5–CO–CH–CO–CH3), (CH3)2Au(bac) (1); (CH3)2Au
(C6H5–CO–CH–CO–CF3), (CH3)2Au(btfa) (2); and (CH3)2Au(C6H5–CO–CH–C(NH)–CH3), (CH3)2Au(i-bac)
(3). The obtained compounds were identified by elemental analysis, 1H NMR and IR-spectroscopy, and
were characterized by DTA and single-crystal X-ray diffraction studies. In compounds 2 and 3, the Au
atom has a square coordination environment AuC2O2 and AuC2NO, respectively.
Received 20 October 2009
Accepted 10 December 2009
Available online 4 January 2010
Keywords:
Organogold(III) precursors, b-Diketonate
dimethylgold
Ó 2010 Elsevier Ltd. All rights reserved.
Volatility
Crystal structure
1. Introduction
depending on terminal substituents and on the type of donor
atoms in the ligand [15]. A topical problem is the synthesis and a
Current interest is growing in gold-containing films and
nanoparticles, which may be used extensively in microelectron-
ics and catalysis [1–4]. One method to produce materials with
specified functional properties is metal–organic chemical vapor
deposition (MOCVD), using volatile metal–organic compounds.
This method allows gold to be deposited as minute particles
[5] or films of various thickness, structure and morphology [6–
9]. The deposition of gold on the surface of solids with a highly
developed surface is an important method for preparing catalyz-
ers with highly dispersed active components and is of great
interest to solve the advanced problems in practical catalysis
[10]. A lack of adequate precursors, however, restricts the study
of gold processes by MOCVD [3]. Compounds used in CVD pro-
cesses must be capable of satisfying several requirements: pro-
nounced vapor pressure at low temperatures, high thermal
stability in condensed and gaseous states, non-toxicity, moisture
resistance and long shelf life.
study of the thermal behavior and structural features, as well as
the correlation between the composition, the crystal structure
and the properties of compounds which may be used as gold pre-
cursors in CVD processes.
We have previously performed complex research on b-diketo-
nates and b-iminoketonates of dimethylgold(III) with various al-
kyl and trifluoroalkyl substituents in the ligand. The syntheses
conditions, properties, structures [16–18] and thermal character-
istics of these complexes in the condensed and gaseous states
[11,15] were studied. To continue investigations of volatile gold-
(III) compounds we have studied volatile dimethylgold(III) com-
plexes based on phenyl-containing ligands, such as (CH3)2Au
(C6H5–CO–CH–CO–CH3), (CH3)2Au(bac) (1); (CH3)2Au(C6H5–CO–
CH–CO–CF3), (CH3)2Au(btfa) (2); and (CH3)2Au(C6H5–CO–CH–
C(NH)–CH3), (CH3)2Au(i-bac) (3). Complex 1 alone is reported in
literature [19], which was obtained by the exchange reaction be-
tween dimethylgold iodide and the Tl(bac) salt. Complexes 2 and
3 were first prepared and studied by the authors of this work.
Data on the structure of complexes 1–3 have not previously been
reported in the Cambridge Structural Database.
Literature data show that of the few known volatile gold com-
pounds, dimethylgold(III) complexes with b-diketones [11–14]
have particular features to be the most suitable for use in gaseous
processes. Those compounds show a wide range of variation in vol-
atility and thermal stability in the condensed and gaseous states,
This paper reports the synthesis of 1–3, data on elemental anal-
ysis, IR and 1H NMR spectra and thermal analysis of the complexes
by the DTA method. The structures of the complexes (CH3)2Au(bt-
fa) (2) and (CH3)2Au(i-bac) (3) were determined. We failed to pre-
pare a single crystal of (CH3)2Au(bac) (1) suitable for structural X-
ray study.
* Corresponding author. Tel.: +7 3833309556; fax: +7 3833309489.
E-mail address: zharkova@che.nsk.su (G.I. Zharkova).
0277-5387/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2009.12.026

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G.I. Zharkova et al. / Polyhedron 29 (2010) 1049–1054
gold atom is coordinated to the oxygen and nitrogen atoms of
2. Results and discussion
the b-iminoketonate ligand and two carbons of the methyl groups
to form a slightly distorted square. The Au–O distance is 0.045 Å
longer than the Au–N distance, the average Au–CH3 bond length
is 2.038 Å, and the chelate bond O–Au–N angle is 90.5°. In the li-
gand, the O–C and N–C bonds are equal to within 0.01 Å, the differ-
2.1. Synthesis and characterization of (CH3)2Au(C6H5–CO–CH–CO–
CH3) (1), (CH3)2Au(C6H5–CO–CH–CO–CF3) (2) and (CH3)2Au(C6H5–
CO–CH–C(NH)–CH3) (3)
ence in the C–C and C–Cve bonds on the side of different
substituents is 0.05 and 0.02 Å, respectively. The significant differ-
Dimethylgold(III) iodide, [(CH3)2AuI]2, was used as the starting
compound for the synthesis of the volatile gold(III) b-diketonates
and b-iminoketonate. This complex was previously prepared from
AuCl3Py and CH3MgI with 21% [20] and 35% [21] yields. We have
developed a new method for the synthesis from KAuCl4 with a
55% yield. The structure of the complex [(CH3)2AuI]2 was first stud-
ied by us [22].
To synthesize dimethylgold chelates, we have used the ligands
1-phenyl-1,3-butane dione, C6H5COCH2COCH3 (Hbac); 1,1,1-tri-
fluoro-4-phenyl-2,4-butanedione, C6H5COCH2COCF3 (Hbtfa); and
1-phenyl-3-amino-2-butene-1-one, C6H5COCHC(NH2)-CH3 (Hi-
bac).
c
ence in the C–C bond lengths, 0.049 Å (that is >3r), may be likely
c
explained by a certain loss of delocalization on the side of the
methyl substituent. The average C–C bond value is 1.39 Å in the
phenyl substituent. The bending of the chelate ring along the
OÁ Á ÁN line is negligible (1°). The phenyl ring plane is turned by
30.1° to the coordination square plane. In the structure, the mole-
cules of the complexes are packed into infinite zig-zag stacks along
the x-axis. A general view of the structure is shown in Fig. 2b. The
gold atom coordination is supplemented to
a bipyramidal
(4 + 1 + 1) coordination with weak contacts to the C atom and to
c
the phenyl ring hydrogen atom of the neighboring complexes,
Complexes (CH3)2Au(bac) (1) and (CH3)2Au(i-bac) (3) were pre-
pared by the reaction between [(CH3)2AuI]2 and the ligand potas-
sium salts. Chloroform and ethanol in a 5:1 ratio were used as
solvents. The fluorinated complex (CH3)2Au(btfa) (2) was prepared
by the reaction of the dimethylgold iodide and the ligand in hep-
tane in the presence of the silver oxide (Ag2O). The compounds
prepared are white low-fusible crystalline substances. These may
be stored for long periods of time at temperatures below zero
and are readily soluble in organic solvents.
the AuÁ Á ÁC and AuÁ Á ÁH distances being 3.52 and 3.35 Å, respec-
c
tively. In the stack, the AuÁ Á ÁAu separations are 5.091 and
6.118 Å, and the Au–Au–Au angle is 77.6° (Fig. 3b). The distances
between the centers of the stacks are >10.5 Å and the shortest
intermolecular HÁ Á ÁH separation is 2.32 Å.
A comparison of the geometric characteristics of the studied
dimethylgold(III) complexes based on a phenyl-containing b-dike-
tone and b-iminoketone (2 and 3) with those obtained by us before
for analogous complexes with various alkyl and trifluoroalkyl sub-
stituents in the ligand [16–18] showed that these values are close
and the bond lengths are within the same ranges: Au–C (2.008–
2.050 Å), Au–O (2.070–2.112 Å) and Au–N (2.051–2.091 Å).
In the IR spectra of the complexes over the 1530–1600 cmÀ1
range there are intense absorption bands of the C–O vibration, con-
firming the chelate type of bonding between the gold atom and the
ligand. In the spectrum of 3 there is a strong typical wide band at
about 3350 cmÀ1, due to valent (N–H) vibrations [23]. In the 1H
m
NMR spectra of complexes 1 and 3, the protons of the CH3 groups
immediately bonded to the gold atoms appear as two signals with
a 1:1 intensity relation, independent of the type of the donor atoms
of the chelation mode. These data and elemental analysis results
confirm the successful preparation of complexes 1–3.
2.3. Thermal study (DTA) of (CH3)2Au(C6H5–CO–CH–CO–CH3) (1),
(CH3)2Au(C6H5–CO–CH–CO–CF3) (2) and (CH3)2Au(C6H5–CO–CH–
C(NH)–CH3) (3)
The thermal study results are listed in Table 1. Upon heating un-
der both helium and hydrogen atmospheres, the complexes behave
alike. The DTA curves show the melting and decomposition effects
in the complexes. Under inert conditions, complex 1 begins to
decompose at 150 °C, while the fluorinated complex 2 decomposes
at a significantly lower temperature. Replacing one oxygen atom
by an NH group in the ligand causes the thermal stability of com-
plex 3 to increase significantly. Upon heating the complexes in a
hydrogen flow, their decomposition point is negligibly lower and
the thermal stability changes with the ligand structure in a similar
manner as under an inert atmosphere. This confirms the fact of the
considerable inertness of dimethylgold b-diketonates to hydrogen
as compared to b-diketonates of platinum group metals, whose
thermal stability sharply decreases under a reducing medium
[16]. Among the established regularities of changing the thermal
stability of dimethylgold(III) chelates depending on the b-diketo-
nate ligand structures, one can note good thermal characteristics
of the b-iminoketonate complex 3. This may be desirable for CVD
processes to obtain gold film covers.
2.2. Structural characterization of 2 and 3
An X-ray structural study revealed that the structure of com-
pound 2 belongs to the molecular type and is built of neutral
(CH3)2Au(btfa) complexes. The structure and the atomic number-
ing scheme are shown in Fig. 1a. The gold atom is coordinated to
two oxygen atoms of the b-diketonate ligand and two carbon
atoms of the methyl groups; the coordination environment is a
slightly distorted AuC2O2 square. The Au–O distances are 2.112 Å,
the average Au–CH3 bond value is 2.014 Å and the chelate O–Au–
O bond angle is 89.4°. In the ligand, the O–C bonds are equal, the
difference in C–C and C–Cve bonds on the side of different substit-
c
uents is 0.02 Å and the average C–C and C–F bond values in the
substituents are 1.39 and 1.33 Å, respectively. The small bending
of the metal cycle along the OÁ Á ÁO line is 3°. The phenyl ligand ring
is turned by 9.4° to the coordination square plane and the torsion
C(5)C(4)C(3)F(3) angle is 26.5°. A general view of the crystal struc-
ture is shown in Fig. 2a. The gold atom coordination is supple-
mented to a pyramidal (4 + 1) coordination with the H atom of
3. Concluding remarks
c
the neighboring complex with a AuÁ Á ÁH separation of 3.42 Å to
form dimeric associates with a AuÁ Á ÁAu separation of 5.859 Å
(Fig. 3a), the remaining AuÁ Á ÁAu separations being >7.15 Å. In the
crystal the shortest intermolecular FÁ Á ÁF and FÁ Á ÁH separations
are 2.99 and 2.80 Å, respectively.
The structure of compound 3 is of the molecular type and com-
prises of neutral (CH3)2Au(i-bac) complexes. The structure is
shown along with the atomic numbering scheme in Fig. 1b. The
We have synthesized and studied volatile dimethylgold(III)
complexes based on phenyl-containing b-diketones and b-iminok-
etone. An improved method for the synthesis of the original
[(CH3)2AuI]2 complex was suggested. A single-crystal X-ray diffrac-
tion study showed that the insertion of Ph and CF3 substituents
into the ligand virtually has no influence on the coordination envi-
ronment of the Au atom in these complexes. The results obtained

G.I. Zharkova et al. / Polyhedron 29 (2010) 1049–1054
1051
a
b
Fig. 1. ORTEP drawing of (CH3)2Au(btfa) (2) (a) and (CH3)2Au(i-bac) (3) (b).
by the DTA method revealed that the replacement of one oxygen
atom by an NH group results in a significant increase in the ther-
mal stability of the b-iminoketonate (CH3)2Au(i-bac) (3) in both in-
ert (Ar) and reduced (H2) atmospheres. In accordance with its
thermal characteristics, this complex may be used as a precursor
in CVD processes.
(CH3)2Au(btfa) (2) and (CH3)2Au(i-bac) (3) were purified by vac-
uum sublimation in a gradient tube oven (P ꢀ 10À2 Torr, T = 50–
250 °C). Elemental analysis was performed with a Carlo-Erba
1106 (Italy) device. Infrared spectra were measured in KBr pellets
with the use of a Scimitar FTS2000 spectrometer. 1H NMR spectra
were recorded on a Bruker MSL300 spectrometer (300 MHz, 25 °C,
ppm) with CDCL3 as the solvent, and chemical shifts were refer-
enced to the proton impurity of the NMR solvent (1H). The thermal
analysis was performed on a Q-1000 Derivatograph (MOM) in open
standard crucibles, in both He and H2 flows (110–120 ml/min), at a
heating rate of 5 K/min and with samples of about 20 mg. Melting
points were determined by a Kofler M.p. apparatus.
4. Experimental
4.1. General considerations
The starting complex, dimethylgold(III) iodide, was prepared
from KAuCl4, synthesized in its turn from hydrogen tetrachloroau-
rate(III) hydrate (Au, 99.9%). Compounds (CH3)2Au(bac) (1),
X-ray intensity data were collected on a Bruker X8Apex CCD dif-
fractometer using standard techniques (x- and u-scans of narrow
frames) at low temperatures and corrected for absorption effects

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G.I. Zharkova et al. / Polyhedron 29 (2010) 1049–1054
a
b
Fig. 2. Projection of the crystal packing of compounds 2 (a) and 3 (b).
Au
Au
3.35
3.42
Au
Au
3.52
Au
a
b
Fig. 3. The additional coordination of the gold atom in the structure of 2 (a) and 3 (b).
Table 1
Results of differential thermal analysis of the complexes.
given in Table 2. All non-hydrogen atoms were refined anisotropi-
cally. Hydrogen atoms Hc and HNH were located from a difference
Compound
M.p.(°C)
Decomp. starting (°C)
map and were included in the refinement. The hydrogen atoms of
the CH3 groups were calculated by geometrical methods. Selected
bond lengths and angles are in Table 3.
DTA/He
DTA/He
DTA/H2
(CH3)2Au(bac) (1)
(CH3)2Au(btfa) (2)
(CH3)2Au(i-bac) (3)
46
66
57
150
80
200
140
75
165
4.2. Synthesis of complex [(CH3)2AuI]2
The Grignard reagent CH3MgI was prepared from magnesium
powder (0.25 g, 10.6 mmol) and iodine methyl (1.51 g, 10.6 mmol)
in 30 ml of absolute diethyl ether, with further addition of 60 ml
hexane, and then the solution was cooled to À30 °C. Dried KAuCl4
salt (1.00 g, 2.65 mmol) was sprinkled onto the cooled solution
(
SADABS). The structures were solved by direct methods and refined
by full-matrix least-squares on F2 using the SHELX97 program set
(Bruker AXS Inc., 2004) [24]. Crystallographic data and details of
single-crystal diffraction experiments for compounds 1–3 are

G.I. Zharkova et al. / Polyhedron 29 (2010) 1049–1054
1053
Table 2
Crystal data and structure refinement for 2 and 3.
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
Unit cell dimensions
a (Å)
C12H12AuF3O2 (2)
44 218
150(2)
monoclinic
P21/n
C12 H16AuNO (3)
387.22
100(2)
monoclinic
P21/c
8.4281(5)
11.1703(7)
13.8825(8)
104.875(2)
1263.16(13)
4
2.325
11.674
7.0700(6)
16.0641(16)
10.8052(11)
105.682(2)
1181.5(2)
4
2.177
12.425
728
b (Å)
c (Å)
b (°)
Volume (Å3)
Z
Dcalc (g/cm3)
Absorption coefficient (mmÀ1
F(000)
)
824
h range for data collection
Index ranges
Reflections collected
Independent reflections
Completeness to h = 25.00° (%)
Refinement method
2.37–28.28
2.33–27.48
À9 6 h 6 11, À14 6 k 6 14, À14 6 l 6 18
À8 6 h 6 4, À20 6 k 6 20, À13 6 l 6 14
9019
8050
2943 [Rint = 0.0377]
94.1
2649 [Rint = 0.0305]
98.1
full-matrix least-squares on F2
2943/0/165
full-matrix least-squares on F2
2649/0/147
Data/restraints/parameters
Goodness-of-fit on F2
1.121
0.954
Final R indices [I>2
r
(I)]
R1 = 0.0321, wR2 = 0.0750
R1 = 0.0476, wR2 = 0.0783
2.215/À1.798
R1 = 0.0246, wR2 = 0.0594
R1 = 0.0359, wR2 = 0.0618
2.391/À1.215
R indices (all data)
Difference map (maximum, minimum, e ÅÀ3
)
Table 3
4.3. Synthesis of (CH3)2Au(C6H5–CO–CH–CO–CH3) (1)
Selected bond lengths (Å) and angles (°) for 2 and 3.
One gram (1.4 mmol) of [(CH3)2AuI]2 was dissolved in 50 ml of
chloroform and mixed with a solution of freshly prepared K(bacac)
salt (2.8 mmol) in a minimal amount of ethyl alcohol. The mixture
was stirred at room temperature for 1 h, the KI residue gradually
dropping out from the solution. The solution was separated from
the precipitated residue and the solvent was eliminated under re-
duced pressure. The isolated product was purified by sublimation
Compound (2)
Au(1)–C(2)
Au(1)–C(1)
Au(1)–O(1)
Au(1)–O(2)
C(4)–O(2)
C(6)–O(1)
C(4)–C(5)
C(4)–C(3)
F(3)–C(3)
F(1)–C(3)
F(2)–C(3)
C(6)–C(5)
C(6)–C(7)
2.012(6)
2.016(6)
2.112(4)
2.113(4)
1.263(7)
1.260(7)
1.386(8)
1.533(9)
1.336(8)
1.329(7)
1.334(9)
1.408(8)
1.509(7)
C(2)–Au(1)–C(1)87.5(3)
C(2)–Au(1)–O(1)
C(1)–Au(1)–O(1)
C(2)–Au(1)–O(2)
C(1)–Au(1)–O(2)
O(1)–Au(1)–O(2)
O(2)–C(4)–C(5)
O(1)–C(6)–C(5)
C(4)–C(5)–C(6)
C(4)–O(2)–Au(1)
F(1)–C(3)–F(2)
F(1)–C(3)–F(3)
F(2)–C(3)–F(3)
F(1)–C(3)–C(4)
F(2)–C(3)–C(4)
F(3)–C(3)–C(4)
C(6)–O(1)–Au(1)
87.5(3)
178.3(2)
90.9(2)
92.2(2)
179.4(3)
89.42(16)
130.8(6)
125.6(5)
125.8(6)
122.1(4)
107.8(6)
106.2(6)
106.5(6)
111.4(5)
110.4(6)
114.2(5)
126.2(4)
under
a reduced pressure. Yield 0.9 g (85%). Anal. Calc. for
C12H15O2Au: C, 37.11; H, 3.86. Found: C, 36.79; H, 3.91%. 1H NMR
(ppm): 1.22 [s, Au–Me], 1.27 [s, Au–Me], 2.17 [s 3H, CH3–CO],
6.00 [s, 1H, CH], 7.3–8.0 [br, 5H, ArH]. IR (cmÀ1): 2911 (m), 1590
(vs), 1558 (vs), 1518 (vs), 1487 (s), 1449 (s), 1389 (vs), 1357 (m),
1283 (m), 1218 (m), 1184 (m), 1111 (w), 1072 (w), 1027 (w),
1000 (w), 949 (m), 857 (w), 828 (w), 798 (m), 774 (s), 715 (s),
684 (s), 623 (s), 545 (w), 462 (w). M.p.: 44–46 °C.
Compound (3)
Au(1)–C(11)
Au(1)–C(12)
Au(1)–N(1)
Au(1)–O(1)
O(1)–C(4)
N(1)–C(2)
C(4)–C(3)
2.036(5)
2.040(5)
2.051(4)
2.096(3)
1.293(6)
1.303(7)
1.376(7)
1.490(6)
1.425(7)
1.511(7)
C(11)–Au(1)–C(12)
C(11)–Au(1)–N(1)
C(12)–Au(1)–N(1)
C(11)–Au(1)–O(1)
C(12)–Au(1)–O(1)
N(1)–Au(1)–O(1)
C(4)–O(1)–Au(1)
C(2)–N(1)–Au(1)
O(1)–C(4)–C(3)
88.9(2)
178.45(18)
92.7(2)
4.4. Synthesis of (CH3)2Au(C6H5–CO–CH–CO–CF3) (2)
Three hundred milligrams (2.8 mmol) of H(btfa) and 0.32 g
(1.4 mmol) of freshly prepared silver oxide (Ag2O) were added to
a solution of [(CH3)2AuI]2 (1 g, 1.4 mmol) in 50 ml of hexane. The
reaction mixture was vigorously stirred at room temperature for
30 min. The solution was separated from the precipitated AgI res-
idue. Then isolation and purification of the complex were per-
formed under the conditions reported above. Yield 1.2 g (92%).
Anal. Calc. for C12H12F3O2Au: C, 32.58; H, 2.71; F, 12.89. Found: C,
32.34; H, 2.52; F, 13.21%. IR (cmÀ1): 2917 (m), 1600 (vs), 1571
(vs), 1532 (s), 1488 (m), 1431 (m), 1316 (m), 1290 (vs), 1251
(m), 1188 (s), 1134 (s), 1066 (m), 997 (w), 937 (w), 771 (m), 696
(m), 659 (m), 586 (w), 536 (w), 444 (vw) 413 (vw). M.p.: 64–65 °C.
88.00(18)
176.84(17)
90.46(15)
123.5(3)
127.2(4)
127.4(4)
123.1(5)
128.3(5)
C(4)–C(5)
C(2)–C(3)
C(2)–C(1)
N(1)–C(2)–C(3)
C(4)–C(3)–C(2)
under an argon flow with vigorous stirring. The reaction mixture
was stirred under an inert atmosphere À10 °C for 0.5 h, then the
temperature was gradually elevated to room temperature. The
complex was isolated from the reaction mixture with slightly acid-
ified water with ice. The organic layer was separated and the water
layer was extracted with hexane three times. The prepared com-
pound was isolated by solvent evaporation with no heating. Yield
0.51 g (55%). The complex [(CH3)2AuI]2 is a colorless substance,
insoluble in water but readily soluble in organic solvents, and the
M.p. is 95–96 °C (with decomposition).
4.5. Synthesis of (CH3)2Au(C6H5–CO–CH–C(NH)–CH3) (3)
A solution of the ligand salt prepared from KOH (0.16 g,
2.8 mmol) and the H(i-bacac) ligand (0.45 g, 2.8 mmol) in 10 ml
of ethanol was added to a solution of [(CH3)2AuI]2 (1 g, 1.4 mmol)
in 50 ml of chloroform. The reaction mixture was stirred for 0.5 h
at 40–45 °C and the KI residue was gradually precipitated from

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G.I. Zharkova et al. / Polyhedron 29 (2010) 1049–1054
the solution. Then the solvent was eliminated under reduced pres-
sure and the dry residue was extracted with hexane. The product
separated was purified by sublimation in a gradient furnace under
reduced pressure. Yield 0.9 g (80%). Anal. Calc. for C12H16NOAu: C,
37.21; H, 4.13; N, 3.61. Found: C, 37.45; H, 4.33; N, 3.78%. 1H NMR
(ppm): 0.92 [s, 3H, Au–Me], 0.93 [s, 3H,Au–Me], 2.06 [s 3H, CH3–
CO], 5.49 [s, 1H, CH], 6.52 [s, 1H, NH], 7.8–8.3 [br, 5H, ArH]. IR
(cmÀ1): 3350 (m), 2923 (s),2852 (m) 1600 (vs), 1527 (vs), 1457
(s), 1406 (m), 1237 (m), 1186 (m), 1072 (m), 1022 (m), 948 (w),
843 (vw), 792 (w), 758 (s), 684 (s), 647 (m), 550 (w), 464 (w),
429 (vw). M.p.: 56–58 °C.
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CCDC 749430 and 749411 contain the supplementary crystallo-
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Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
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Acknowledgements
[24] Bruker AXS Inc., APEX2 (Version 1.08), SAINT (Version 7.03), SADABS (Version 2.11)
and SHELXTL (Version 6.12), Bruker Advanced X-ray Solutions, Madison,
Wisconsin, USA, 2004.
The authors thank Dr. N. Kuratieva and A. Smolentsev for the
supplied single- crystal X-ray diffraction data.