V. W.-W. Yam et al.
sidearm 1 cm fluorescence cuvette and were sealed from the atmosphere
by a Rotaflo HP6/6 quick-release Teflon stopper. Solutions were rigor-
ously degassed on a high-vacuum line in a two-compartment cell with no
less than four successive freeze-pump-thaw cycles. Cyclic voltammetric
measurements were performed by using a CH Instruments model CHI
[Au
(ppy)Cl
cording to the general procedure and was obtained as orange crystals
A
H
U
G
R
N
N
(ppy)(CꢀCꢁC
6
H
4
ꢁCF
3
-p)
2
] 3: Complex 3 was prepared from [Au-
A
T
N
T
E
N
N
2
] (127 mg) and 4-trifluoromethylphenylacetylene (204 mg) ac-
1
(yield: 58 mg, 28%). H NMR (400 MHz, CD
2H; ppy), 7.48 (m, 1H; ppy), 7.57 (m, 4H; -C
2
Cl
2
, 298 K): d=7.40 (m,
-),
6
H
4
-), 7.65 (m, 4H; -C H
6 4
6
00 A electrochemical analyzer. The electrolytic cell used was a conven-
7.66 (m, 1H; ppy), 7.94 (d, 8.1 Hz, 1H; ppy), 8.09 (dt, J=1.3 and 7.3 Hz,
1H; ppy), 8.17 ppm (dd, J=1.3 and 7.3 Hz; ppy); IR (KBr): n˜ =2136,
tional two-compartment cell. Electrochemical measurements were per-
formed in dichloromethane solutions with TBAH (0.1m) as the support-
ing electrolyte at room temperature. The reference electrode was a Ag/
ꢁ
1
+
2166 cm (n˜
A
H
U
G
E
N
N
(CꢀC)); positive FABMS: m/z: 689 [M] ; elemental analysis
calcd (%) for C29
2.36, N 2.08.
H
6
16NF Au: C 50.52, H 2.34, N 2.03; found: C 50.35, H
3
AgNO (0.1m in acetonitrile) electrode, and the working electrode was a
glassy carbon electrode (CH Instruments) with a platinum wire as the
counter electrode. The working electrode surface was first polished with
a 1 mm alumina slurry (Linde), followed by a 0.3 mm alumina slurry, on a
microcloth (Buehler). Treatment of the electrode surfaces was as report-
ꢀ ꢁ
ꢁ
[
Au
A
H
U
G
R
N
N
(ppy)(C C C
6
H
4
NH
2
-p)
2
] 4: Complex 4 was prepared from [Au-
A
H
U
G
E
N
N
2
] (127 mg) and 4-aminophenylacetylene (141 mg) according to
the general procedure and was obtained as dark-orange crystals (yield:
1
9
-
5
7
6 mg, 55%). H NMR (400 MHz, [D
NH ), 5.30 (s, 2H; -NH ), 6.56 (m, 4H; -C
.6 Hz, 4H; -C -), 7.41 (m, 2H; ppy), 7.75 (m, 1H; ppy), 8.01 (d, J=
.6 Hz, 1H; ppy), 8.16 (d, J=7.6 Hz, 1H;, ppy), 8.34 (m, 2H; ppy),
6
]DMSO, 298 K): d=5.24 (s, 2H;
[
26a]
+/0
ed previously.
as the internal reference.
The ferrocenium/ferrocene couple (FeCp
2
) was used
2
2
6 4
H
-), 7.17 (dd, J=2.5 and
[
26b]
All solutions for electrochemical studies
6 4
H
were deaerated with prepurified argon gas just before measurements.
ꢁ1
Crystal-structure determination: Single crystals of 1, 6, 11, 12, and 15
suitable for X-ray diffraction studies were grown by layering of n-hexane
onto a concentrated dichloromethane solution of the respective com-
plexes. The X-ray diffraction data were collected on a Bruker Smart
CCD 1000 using graphite-monochromatized MoKa radiation (l=
9.57 ppm (d, J=5.6 Hz, ppy); IR (KBr): n˜ =2129, 2191 cm ( n˜
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(CꢀC));
+
positive FABMS: m/z: 584 [M] ; elemental analysis calcd (%) for
1
27 20 3 2 2
C H N Au· = H O: C 54.74, H 3.57, N 7.09; found: C 54.81, H 3.40, N
7.09.
[Au(ppy)
ACHTUNGERTN(NUNG ppy)Cl ] (127 mg) and trimethylsilylacetylene (118 mg) according to the
A
H
U
G
E
N
N
A
H
U
G
R
N
U
G
3 3 2
ACHTUNGTRENNU(NG CH ) ) ] 5: Complex 5 was prepared from [Au-
0
.71073 ꢁ). The images were interpreted and intensities were integrated
2
[27]
by using the DENZO program.
methods employing the SHELXS-97 program.
The structure was solved by direct
general procedure and was obtained as pale-yellow crystals (yield: 20 mg,
12%). H NMR (400 MHz, CD Cl , 298 K): d=0.23 (s, 9H; -Si ACHTUNGTRENNUNG( CH ) ),
2 2 3 3
0.25 (s, 9H; -Si ACHUTNGTNERNUG( CH ) ), 7.31–7.43 (m, 3H; ppy), 7.69 (dd, J=1.4 and
3 3
7.5 Hz, 1H; ppy), 7.91 (d, J=8.1 Hz, 1H; ppy), 8.06 (m, 1H; ppy), 8.13
(dd, J=1.4 and 7.5 Hz, 1H; ppy), 9.58 ppm (d, J=5.7 Hz, 1H; ppy); IR
[
28]
1
Full-matrix least-
2
squares refinement on F was used in the structure refinement. The posi-
tions of H atoms were calculated based on the riding mode with thermal
parameters equal to 1.2 times those of the associated C atoms and par-
ticipated in the calculation of final R-indices. In the final stage of the
least-squares refinement, all non-hydrogen atoms were refined anisotrop-
ically. CCDC-783733 (1), CCDC-783734 (6), CCDC-783735 (11), CCDC-
ꢁ
1
+
(KBr): n˜ =2075, 2098 cm ( n˜ ACHTGNUTRENNUNG
elemental analyses calcd (%) for C H NSi Au· = H O: C 45.48, H 4.71,
1
2
1
26
2
2
2
N 2.67; found: C 45.12, H 4.91, N 2.53.
Au -p) ] 6: Complex 6 was prepared from [Au-
(ptpy)(CꢀCꢁC ꢁOCH
(ptpy)Cl ] (131 mg) and 4-methoxyphenylacetylene (159 mg) according
to the general procedure and was obtained as yellow crystals (yield:
7
83736 (12), and CCDC-783737 (15) contain the supplementary crystallo-
[
A
H
U
G
R
N
U
G
6
H
4
3
2
graphic data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via www.ccdc.cam.a-
c.uk/data_request/cif.
A
H
U
G
R
N
U
2
1
9
6 mg, 60%). H NMR (300 MHz, CDCl
3 3
, 298 K): d=2.41 (s, 3H; -CH ),
Synthesis
3.82 (s, 6H; -OCH ), 6.85 (m, 4H; -C H -), 7.14 (d, J=7.9 Hz, 1H; ptpy),
3
6
4
General procedure for syntheses of dialkynylgold
A
H
U
G
R
N
N
(III) complexes: n-Bu-
7.36 (t, J=7.2 Hz, 1H; ptpy), 7.57–7.37 (m, 5H; ptpy and -C
6 4
H -), 7.83
tyllithium (1.44 mmol, 1.6m in hexanes) was added to a solution of
alkyne (1.20 mmol) in tetrahydrofuran (20 mL) under a nitrogen atmos-
phere in a dropwise manner at ꢁ788C. The resulting mixture was stirred
(d, J=8.0 Hz, 1H; ptpy), 7.99 (t, 7.5 Hz, 1H; ptpy), 8.11 (s, 1H; ptpy),
ꢁ
1
9.66 ppm (d, J=5.7 Hz, 1H; ptpy); IR (KBr): n˜ =2130, 2163 cm ( n˜ ACHTUNGTRENNUNG
(C
ꢀ
+
C)); positive FABMS: m/z: 532 [M] ; elemental analysis calcd (%) for
1
for 5 min and transferred to a suspension of [Au
A
H
U
T
E
N
N
(C^N)Cl
2
] (0.30 mmol)
C
30
H
24NO
2
Au· =
3.87, N 2.31.
[Au
(ptpy)(CꢀCꢁC H ꢁC H -p) ] 7: Complex 7 was prepared from [Au-
(ptpy)Cl ] (131 mg) and 4-n-butylphenylacetylene (190 mg) according to
2 3
CH OH: C 56.93, H 4.07, N 2.18; found: C 56.90, H
in tetrahydrofuran (30 mL). The reaction mixture was stirred for 3 h at
room temperature. The crude product, which was obtained upon removal
of solvent from the reaction mixture, was subjected to purification by
column chromatography on silica gel by using dichloromethane as the
eluent. Subsequent recrystallization by slow diffusion of diethyl ether
vapor into the concentrated dichloromethane solution of the compound
gave the resulting complex as yellow to orange crystals.
AHCTUNGTRENNUNG
6
4
4
9
2
AHCTUNGTRENNUNG
2
the general procedure and was obtained as yellow crystals (yield: 61 mg,
1
39%). H NMR (400 MHz, CD Cl , 298 K): d=0.94 (m, 6H; -CH ), 1.38
2
2
3
(m, 4H; -CH -), 1.59 (m, 4H; -CH -), 2.38 (s, 3H; -CH ), 2.61 (m, 4H;
2
2
3
-CH -), 7.15 (m, 5H; ptpy and -C H -), 7.36 (m, 1H; ptpy), 7.43 (dd, J=
2
6
4
(ppy)(CꢀCꢁC
H
ꢁOCH
3 2
-p) ] 1: Complex 1 was prepared from [Au-
8
8
1
6 4
.1 and 4.7 Hz, 4H; -C H -), 7.58 (d, J=8.1 Hz, 1H; ptpy), 7.85 (d, J=
[
Au
(ppy)Cl
the general procedure and was obtained as yellow crystals (yield: 61 mg,
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
6
4
.1 Hz, 1H; ptpy), 7.99 (m, 2H; ptpy), 9.57 ppm (dd, J=1.1 and 4.7 Hz,
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
2
] (127 mg) and 4-methoxyphenylacetylene (159 mg) according to
ꢁ
1
H; ptpy); IR (KBr): n˜ =2113, 2167 cm ( n˜
A
H
U
G
R
N
N
(CꢀC)); positive FABMS:
+
1
m/z: 522 [MꢁCꢀCC H ꢁC H ] ; elemental analysis calcd (%) for
3
(
3%). H NMR (400 MHz, CDCl
m, 4H; -C -), 7.39 (m, 1H; ppy), 7.41 (m, 2H), 7.50–7.56 (m, 4H;
-), 7.67 (d, J=5.7 Hz, 1H; ppy), 7.90 (d, J=6.0 Hz, 1H; ppy), 8.06
3
, 298 K): d=3.82 (s, 6H; -OCH
3
), 6.85
6
4
4
9
C
36
H
36NAu: C 63.62, H 5.34, N 2.06; found: C 63.80, H 5.56, N 2.29.
(CꢀCꢁSi
(ptpy) (CH ) ] 8: Complex was prepared from [Au-
ACHTUNGERTN(NUNG ptpy)Cl ] (131 mg) and trimethylsilylacetylene (118 mg) according to the
6 4
H
-
C
6
H
4
[Au
A
H
U
G
R
N
U
G
A
H
U
G
R
N
N
A
H
U
G
R
N
U
G
8
3
3
(
4
t, J=6.5 Hz, 1H; ppy), 8.30 (d, J=7.5 Hz, 1H; ppy), 9.71 ppm (d, J=
.8 Hz, 1H; ppy); IR (KBr): n˜ =2120, 2167 cm ( n˜
FABMS: m/z: 614 [M] ; elemental analysis calcd (%) for C29
2
ꢁ1
A
H
U
G
R
N
N
(CꢀC)); positive
general procedure and was obtained as pale-yellow crystals (yield: 25 mg,
15%). H NMR (400 MHz, CD Cl , 298 K, relative to Me Si): d=0.23 (s,
+
1
H
22NO
2
Au :
2
2
4
C 56.78, H 3.61, N 2.28; found: C 56.94, H 3.87, N 2.32.
9H; -Si
.9 Hz, 1H; ppy), 7.35 (t, J=6.1 Hz, 1H; ppy), 7.57 (d, J=7.9 Hz, 1H;
ppy), 7.84 (d, J=7.9 Hz, 1H; ppy), 7.97 (s, 1H; ppy), 8.02 (m, 1H; ppy),
3 3 3 3 3
ACHTUNGTRENNUNG( CH ) ), 0.27 (s, 9H; -Si ACHTNUTGERNUN(G CH ) ), 2.37 (s, 3H; -CH ), 7.14 (d, J=
(ppy)(CꢀCꢁC
H
ꢁC
2 5 2
H -p) ] 2: Complex 2 was prepared from [Au-
7
[
Au
(ppy)Cl
general procedure and was obtained as yellow crystals (yield: 51 mg,
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
6
4
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
2
] (127 mg) and 4-ethylphenylacetylene (156 mg) according to the
ꢁ
1
9
.54 ppm (d, J=4.9 Hz, 1H; ppy); IR (KBr): n˜ =2075, 2098 cm ( n˜
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(Cꢀ
+
1
C)); positive FABMS: m/z: 560 [M] ; elemental analysis calcd (%) for
2
(
8%). H NMR (400 MHz, CDCl
m, 4H; -CH -), 7.14 (m, 4H; -C
-), 7.66 (d, J=7.0 Hz, 1H; ppy), 7.89 (m, 1H; ppy), 8.04 (s, 1H;
ppy), 8.27 (d, J=7.0 Hz, 1H; ppy), 9.67 ppm (s, 1H; ppy); IR (KBr): n˜ =
3
, 298 K): d=1.24 (s, 6H; -CH
3
), 2.65
1
22 2 2 2
C H28NSi Au· = H O: C 46.47, H 5.14, N 2.46; found: C 46.50, H 5.07, N
2
6 4
H -), 7.38 (m, 3H; ppy), 7.51 (m, 4H;
2
.46.
[Au
(tbppy)(CꢀCꢁC H ꢁOCH -p) ] (tbppy=2-(p-(tert-butyl)phenyl)pyri-
2
dine) 9: Complex 9 was prepared from [Au ACHUTNGRENNUG( tbppy)Cl ] (143 mg) and 4-
6 4
-C H
AHCTUNGTRENNUNG
6
4
3
2
ꢁ
1
+
2
136, 2163 cm (n˜
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(CꢀC)); positive FABMS: m/z: 609 [M] ; elemental
1
analysis calcd (%) for C31
H
26NAu· =
2
C
5
H
12: C 62.32, H 5.00, N 2.17;
methoxyphenylacetylene (159 mg) according to the general procedure
1
found: C 62.31, H 4.60, N 2.52.
and was obtained as orange crystals (yield: 42 mg, 21%). H NMR
140
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 130 – 142