Bartolomé et al.
(0.090 g, 0.2 mmol) in dichloromethane (10 mL). After 15 min of
stirring at room temperature, the volatiles were pumped off and
the pale-gray residue was washed with n-hexane (3 × 5 mL) and
crystallized from dichloromethane/n-hexane. The colorless crystals
obtained were decanted, washed with n-hexane (3 × 5 mL), and
vacuum-dried, yielding 0.067 g (71%). IR: 2225s ν(CtN). 1H NMR
(300 MHz, CDCl3, 295 K): δ 8.63 (ddd, J ) 4.9, 0.9, and 1.8 Hz,
H3, CNC5H4N, 1H), 7.97 (td, J ) 7.8 and 1.8 Hz, H5, CNC5H4N,
1H), 7.59 (m, H4 and H6, CNC5H4N, 2H). 19F NMR (282.5 MHz,
CDCl3, 295 K): δ -116.38 (m, 2Fortho), -157.59 (t, J ) 20.1 Hz,
1Fpara), -162.73 (m, 2Fmeta). Anal. Calcd for C12H4N2F5Au: C,
30.79; H, 0.86; N, 5.98. Found: C, 30.86; H, 0.95; N, 5.56.
[Au(Fmes)(CNPy-2)] (3). 2-CNPy (0.29 mmol, 2.9 mL, 0.1 M
solution in acetone) was added to a solution of [Au(Fmes)(tht)]
(0.150 g, 0.26 mmol) in dichloromethane (15 mL). After 15 min
of stirring at room temperature, the volatiles were pumped off and
the white residue was washed with n-hexane (3 × 5 mL) and
crystallized from dichloromethane/n-hexane. The colorless crystals
obtained were decanted, washed with n-hexane (3 × 5 mL), and
vacuum-dried, yielding 0.123 g (81%). IR: 2216s ν(CtN), 684w
[Au(Fmes){C(NEt2)(NHPy-2)}] (6). Diethylamine (0.17 mmol,
18 µL) was added to a solution of 3 (0.050 g, 0.86 mmol) in
dichloromethane (10 mL). After 5 min of stirring at room
temperature, the IR of the solution did not show CN absorption.
Then the volatiles were pumped off, and the residue was crystallized
from dichloromethane/n-hexane. The white solid was decanted,
washed with n-hexane (3 × 5 mL), and dried under vacuum,
1
yielding 0.042 g (75%). H NMR (300 MHz, CDCl3, 295 K): δ
8.56 (d, J ) 8.3 Hz, 1H, NHC5H4N), 8.35 (br, 1H, NHC5H4N),
8.31 (m, 1H, NHC5H4N), 7.99 (s, 2H, Fmes), 7.71 (tm, J ) 7.9
Hz, 1H, NHC5H4N), 7.15 (m, 1H, NHC5H4N), 4.21 (q, J ) 7.2
Hz, 2H, N(CH2CH3)2), 3.57 (q, J ) 7.4 Hz, 2H, N(CH2CH3)2),
1.42 (t, J ) 7.2 Hz, 3H, N(CH2CH3)2), 1.40 (t, J ) 7.4 Hz, 3H,
N(CH2CH3)2). 19F NMR (282.5 MHz, CDCl3, 295 K): δ -60.39
(s, 6F, o-CF3), -63.13 (s, 3F, p-CF3). Anal. Calcd for
C19H17N3F9Au: C, 34.82; H, 2.61; N, 6.41. Found: C, 35.14; H,
2.32; N, 6.07.
[AuCl{C(NHMe)(NHPy-2)}] (7). Methylamine (0.3 mmol, 25.5
µL, 40% solution in water) was added to a solution of 1 (0.100 g,
0.3 mmol) in dichloromethane (15 mL). After 5 min of stirring at
room temperature, the IR solution did not show CN absorption.
The volatiles were pumped off, and the pale-violet residue was
crystallized from dichloromethane/n-hexane. The colorless crystals
obtained were washed with n-hexane (3 × 5 mL) and vacuum-
1
ν(Au-R). H NMR (300 MHz, CDCl3, 295 K): δ 8.64 (dm, J )
4.8 Hz, H3, CNC5H4N, 1H), 8,04 (s, 2H, Fmes), 7.97 (td, J ) 7.8
and 1.7 Hz, H5, CNC5H4N, 1H), 7.59 (m, H4 and H6, CNC5H4N,
2H). 19F NMR (282.5 MHz, CDCl3, 295 K): δ -60.55 (s, 6F,
o-CF3), -63.26 (s, 3F, p-CF3). Anal. Calcd for C15H6N2F9Au: C,
30.95; H, 1.04; N, 4.81. Found: C, 30.85; H, 0.96; N, 4.72.
[AuCl{C(NEt2)(NHPy-2)}] (4). Diethylamine (0.60 mmol, 0.044
g, 61.6 µL) was added to a solution of 1 (0.100 g, 0.30 mmol) in
dichloromethane (15 mL). After 15 min of stirring at room
temperature, the solution was filtered through a small column of
Kieselgur and silica gel and crystallized from dichloromethane/n-
hexane. The colorless crystals thus obtained were decanted, washed
with n-hexane (3 × 5 mL), and dried under vacuum, yielding 0.092
1
dried, yielding 0.079 g (74%). H NMR (300 MHz, CDCl3, 295
K): δ 12.40 (br, 1H, NHCH3), 9.59 (br, 1H, NHC5H4N), 8.22 (dm,
J ) 5.2 Hz, 1H, NHC5H4N), 7.73 (m, 1H, NHC5H4N), 7.21 (dm,
J ) 8.3 Hz, 1H, NHC5H4N), 7.07 (m, 1H, NHC5H4N), 3.41 (d, J
) 4.8 Hz, 3H, NHCH3). 1H NMR (300 MHz, Me2CO-d6, 295 K):
δ 12.50 (br, 1H, NHCH3), 10.15 (br, 1H, NHC5H4N), 8.34 (dm, J
) 4.8 Hz, 1H, NHC5H4N), 7.93 (m, 1H, NHC5H4N), 7.25 (m, 2H,
NHC5H4N), 3.40 (d, J ) 4.8 Hz, 3H, NHCH3). Anal. Calcd for
C7H9N3AuCl: C, 22.87; H, 2.47; N, 11.43. Found: C, 23.25; H,
2.25; N, 11.19. UV-vis (CH2Cl2): λ 285 (ꢀ 2.66 × 104), 247.5 (ꢀ
3.65 × 104). λex (KBr): 334. λem (KBr): 470. λex (CH2Cl2): 345.
λem (CH2Cl2): 409.
1
g (75%). H NMR (300 MHz, CDCl3, 295 K): δ 8.50 (d, J ) 8.4
Hz, NHC5H4N, 1H), 8.30 (dm, J ) 1.4 Hz, NHC5H4N, 1H), 8.13
(br, NHC5H4N, 1H), 7.78 (m, NHC5H4N, 1H), 7.18 (m, H4,
NHC5H4N, 1H), 4.13 (q, J ) 7.2 Hz, N(CH2CH3)2, 2H), 3.54 (q,
J ) 7.3 Hz, N(CH2CH3)2, 2H), 1.4 (t, J ) 7.2 Hz, N(CH2CH3)2,
3H), 1.37 (t, J ) 7.3 Hz, N(CH2CH3)2, 3H). Anal. Calcd for
C10H15N3AuCl: C, 29.32; H, 3.69; N, 10.26. Found: C, 29.68; H,
3.22; N, 9.98. UV-vis (CH2Cl2): λ 277.0 (ꢀ 1.44 × 103), 249.5 (ꢀ
1.57 × 103), 227.0 (ꢀ 1.18 × 103). λex (KBr): 383. λem (KBr): 562.
λex (CH2Cl2): 364. λem (CH2Cl2): 457.
[Au(C6F5){C(NEt2)(NHPy-2)}] (5). Diethylamine (0.43 mmol,
44.6 µL) was added to a solution of 2 (0.100 g, 0.21 mmol) in
dichloromethane (15 mL). After 15 min of stirring at room
temperature, the IR of the solution did not show CN absorption.
Then the volatiles were pumped off, and the residue was crystallized
from dichloromethane/n-hexane. The white solid obtained was
decanted, washed with n-hexane (3 × 5 mL), and dried under
vacuum, yielding 0.081 g (71%). 1H NMR (300 MHz, CDCl3, 295
K): δ 8.78 (dm, J ) 8.2 Hz, 1H, NHC5H4N), 8.32 (m, 1H,
NHC5H4N), 8.17 (br, 1H, NHC5H4N), 7.80 (m, 1H, NHC5H4N),
7.17 (m, 1H, NHC5H4N), 4.21 (q, J ) 7.2 Hz, 2H, N(CH2CH3)2),
3.55 (q, J ) 7.4 Hz, 2H, N(CH2CH3)2), 1.47 (t, J ) 7.2 Hz, 3H,
N(CH2CH3)2), 1.39 (t, J ) 7.4 Hz, 3H, N(CH2CH3)2). 19F NMR
(282.5 MHz, CDCl3, 295 K): δ -117.00 (m, 2Fortho), -160.08 (t,
J ) 20.1 Hz, 1Fpara), -163.42 (m, 2Fmeta). Anal. Calcd for
C16H15N3F5Au: C, 35.50; H, 2.79; N, 7.76. Found: C, 35.46; H,
2.65; N, 7.49. UV-vis (CH2Cl2): λ 276.5 (ꢀ 1.29 × 104), 248.5 (ꢀ
1.82 × 104), 228.5 (ꢀ 1.18 × 104). λex (KBr): 360. λem (KBr): 470.
λex (CH2Cl2): 323. λem (CH2Cl2): 438, 477, 508 (sh).
[Au(C6F5){C(NHMe)(NHPy-2)}] (8). Methylamine (0.34 mmol,
29.5 µL, 40% solution in water) was added to a solution of 2 (0.080
g, 0.17 mmol) in dichloromethane (10 mL). After 30 min of stirring
at room temperature, the volatiles were pumped off and the white
residue was washed with n-hexane (3 × 5 mL), yielding 0.066 g
(78%). 1H NMR (300 MHz, CDCl3, 295 K): δ 12.50 (br, NHCH3,
1H), 8.27 (dd, J ) 1.4 and 4.8 Hz, H3, NHC5H4N, 1H), 8.01 (br,
NHC5H4N, 1H), 7.76 (m, H5, NHC5H4N, 1H), 7.11 (m, H4,
NHC5H4N, 1H), 6.85 (dm, J ) 8.2 Hz, H6, NHC5H4N, 1H), 3.52
(d, J ) 4.8 Hz, NHCH3, 3H). 19F NMR (282.5 MHz, CDCl3, 295
K): δ -117.02 (m, 2Fortho), -158.82 (t, J ) 20.3 Hz, 1Fpara),
1
-163.22 (m, 2Fmeta). H NMR (300 MHz, Me2CO-d6, 295 K): δ
12.67 (br, 1H, NHCH3), 10.27 (br, 1H, NHC5H4N), 8.31 (dm, J )
3.6 Hz, 1H, NHC5H4N), 7.90 (m, 1H, NHC5H4N), 7.26 (d, J ) 8.3
Hz, 1H, NHC5H4N), 7.21 (m, 1H, NHC5H4N), 3.50 (d, J ) 4.7
Hz, 3H, NHCH3). 19F NMR (282.5 MHz, Me2CO-d6, 295 K): δ
-115.60 (m, 2Fortho), -160.57 (t, J ) 20 Hz, 2Fpara), -163.62 (m,
2Fmeta). Anal. Calcd for C13H9N3AuF5: C, 31.28; H, 1.82; N, 8.42.
Found: C, 31.28; H, 1.59; N, 8.11. UV-vis (KBr): 297.5 (0.646),
267 (0.625). UV-vis (CH2Cl2): λ 285.0 (ꢀ 7.43 × 103), 248.0 (ꢀ
1.21 × 104). λex (KBr): 342. λem (KBr): 484. λex (CH2Cl2): 395.
λem (CH2Cl2): 479.
[Au(Fmes){C(NHMe)(NHPy-2)}] (9). Methylamine (0.20 mmol,
18 µL, 40% solution in water) was added to a solution of 3 (0.060
g, 0.10 mmol) in dichloromethane (10 mL). After 5 min of stirring
at room temperature, the IR of the solution did not show the
isocyanide absorption. Then the volatiles were pumped off, and
1622 Inorganic Chemistry, Vol. 47, No. 5, 2008