E. Cerrada, M. Laguna, N. Lardíes
FULL PAPER
mixture was stirred for a further 6 h. The solvent was evaporated
under vacuum to 5 mL, and hexane (30 mL) was added to precipi-
tate the corresponding product, which was filtered off and washed
δ = 7.68–7.47 (m, 20 H), 2.55 (s, 6 H), 2.14 (d, J = 9.9 Hz, 6 H)
3
1
1
3
ppm. P{ H} NMR (CDCl ): δ = 21.9 (s) ppm. IR (KBr): ν˜ =
–
1
+
2131 [ν(CϵC)] cm . MS (LSIMS ): m/z (%) = 1223 (32), 1023
1
+
+
with water. 9c: yellow solid (356 mg, 83%). H NMR ([D
6
3
]dmso):
(16), 1012 (7) [M + H] , 597 (38), 397 (100) [AuPPh
NP (1011.40): calcd. C 43.90, H 3.26, N 1.38, S 6.33;
]dmso): δ = 6.2 (s) ppm. IR (KBr): ν˜ = 2126 [ν(CϵC)] found C 43.53, H 2.93, N 1.75, S 6.36. 11e: brown solid (158 mg,
2
Me] .
1
1
δ = 7.82–7.09 (m, 14 H), 1.92 (d, J = 11.3 Hz, 12 H) ppm. P{ H}
NMR ([D
cm . MS (LSIMS ): m/z (%) = 1037 (10), 899 (6), 705 (9), 473 (33)
C
37
H33Au
2
2 2
S
6
–1
+
1
43%). H NMR (CDCl
3
): δ = 7.49 (m, 31 H), 2.56 (s, 6 H) ppm.
+
–1
+
[Au(PPhMe
2 2 2 2 2
) ] . C26H26Au P S (858.26): calcd. C 36.35, H 3.03,
IR (KBr): ν˜ = 2132 [ν(CϵC)] cm . MS (LSIMS ): m/z (%) = 1541
+
+
S 7.46; found C 35.75, H 2.71, S 7.59. 9d: yellow solid (279 mg,
(50), 1224 (30) [M
Au NS (1223.48): calcd. C 46.10, H 3.02, N 1.14, S
]dmso): δ = 4.0 (s) ppm. IR (KBr): 5.23; found C 45.81, H 2.63, N 1.50, S 5.69.
+
3 2
H] , 809 (100) [Au(AsPh ) ] .
1
7
1
6%). H NMR ([D
6
]dmso): δ = 7.11 (s, 4 H), 1.63 (d, J = 11.4 Hz,
C
47
H37As
2
2
2
8 H) ppm. 31P{ H} NMR ([D
1
6
–1
+
ν˜ = 2132 [ν(CϵC)] cm . MS (LSIMS ): m/z (%) = 851 (100)
+
+
Synthesis of [Au
4 2 2
(S–CϵC–CϵC–S) L ] {L = dppm (12a), dppe
[
S(AuPMe
3 3 2 2 2
) ] , 775 (36), 734 (18) [M] . C16H22Au P S (734.42):
(
12b)}: To a solution of compound 6e (333 mg, 0.15 mmol) in dry
calcd. C 26.14, H 3.00, S 8.71; found C 26.50, H 2.82, S 8.73. 9e:
1
thf (15 mL) was added dppm (57 mg, 0.15 mmol) or dppe (60 mg,
0.15 mmol). The reaction mixture was stirred under an argon atmo-
sphere for 12 h. The solvent was removed under vacuum to a vol-
ume of 5 mL, and diethyl ether was added to precipitate the corre-
3
pale brown solid (430 mg, 72%). H NMR (CDCl ): δ = 7.49–7.18
–
1
+
(
(
C
m) ppm. IR (KBr): ν˜ = 2134 [ν(CϵC)] cm . MS (LSIMS ): m/z
+
+
%) = 1540 (10), 1194 (7) [M] , 809 (100) [Au(AsPh
Au (1194.76): calcd. C 46.24, H 2.87, S 5.38; found
C 45.96, H 2.90, S 5.30.
3 2
) ] , 503 (70).
46
H34As
2
2 2
S
1
sponding product. 12a: red solid (119 mg, 89%). H NMR
3
1
1
(
CDCl
3
): δ = 7.88–7.26 (m, 40 H), 4.72 (s, 4 H) ppm. P{ H}
): δ = 33.0 (s) ppm. IR (KBr): ν˜ = 2109 (w), 2025
Synthesis of [Au -(2,7)-(S–CϵC–C15
10a), PPh Me (10b), AsPh (10e)}: To an ice-cooled solution of
,7-bis(1,2,3-thiadiazol-4-yl)-9,9-dimethylfluorene (4) (90 mg,
2
2 3
H12–CϵC–S)L ] {L = PPh
NMR (CDCl
(
1
3
(
2
3
–1
+
m) [ν(CϵC)] cm . MS (LSIMS ): m/z (%) = 1818 (8), 1289 (22),
2
0
0
+
162 (100) [Au
2 2
(dppm) ] , 963 (43), 579 (45), 383 (35).
.25 mmol) in dry thf (15 mL) was added tBuOK (62 mg,
.55 mmol). The mixture was stirred under an argon atmosphere
58 4 4 4
C H44Au P S
3
(1781.15): calcd. C 39.11, H 2.49, S 7.20; found C
1
8.92, H 2.21, S 7.62. 12b: green solid (129 mg, 95%). H NMR
for 1 h, and then [AuCl(PPh
AuCl(PPh Me)] (186 mg, 0.43 mmol) or [AuCl(AsPh
.43 mmol) was added. The mixture was stirred for a further 6 h.
3
)] (212 mg, 0.43 mmol),
31
1
(CDCl
3
): δ = 7.69–7.18 (m, 40 H), 2.46 (s, 8 H) ppm. P{ H}
[
2
3
)] (232 mg,
NMR (CDCl
3
): δ = 21.5 (s) ppm. IR (KBr): ν˜ = 2035 [ν(CϵC)]
0
–1
+
+
cm . MS (LSIMS ): m/z (%) = 994 (100) [Au(dppe)
(1809.20): calcd. C 39.83, H 2.67, S 6.85; found C
9.43, H 2.95, S 6.36.
2
] , 567 (29).
The solvent was evaporated under vacuum to a volume of 5 mL,
and hexane (30 mL) was added to precipitate the corresponding
product, which was filtered off and washed with water. 10a: yellow
60 4 4 4
C H48Au P S
3
1
4 2 6 4 2 2
Synthesis of [Au {1,3-(S–CϵC) –C H } L ] {L = dppm (13a), dppe
solid (238 mg, 78%). H NMR ([D
6
]dmso): δ = 7.51–733 (m, 36
3
1
1
(13b)}: To a solution of compound 9e (597 mg, 0.42 mmol) in dry
thf (30 mL) was added dppm (161 mg, 0.42 mmol) or dppe
(167 mg, 0.42 mmol). The reaction mixture was stirred under an
argon atmosphere for 12 h. The precipitate was filtered off and
H), 1.39 (s, 6 H) ppm. P{ H} NMR ([D ]dmso): δ = 38.1 (s) ppm.
6
–1
+
IR (KBr): ν˜ = 2136 [ν(CϵC)] cm . MS (LSIMS ): m/z (%) = 1409
71), 1223 (12) [M] , 721 (51), 459 (100) [AuPPh
+
+
(
3 2 2 2
] . C55H42Au P S
(
1222.64): calcd. C 53.99, H 3.44, S 5.23; found C 53.60, H 3.15, S
.77. 10b: orange solid (212 mg, 77%). 1H NMR (CDCl
washed with diethyl ether to afford the corresponding compound.
4
7
3
): δ =
.67–7.23 (m, 26 H), 2.17 (d, J = 9.6 Hz, 6 H), 1.39 (s, 6 H) ppm.
1
1
3a: yellow solid (227 mg, 56%). H NMR (dmso): δ = 7.50–7.15
–
1
3
1
1
(m, 48 H), 3.72 (m, 4 H) ppm. IR (KBr): ν˜ = 2131 [ν(CϵC)] cm .
MS (LSIMS ): m/z (%) = 1935 (7) [M] , 1738 (7) [M – Au] , 1161
(100) [Au (dppm) ] . C H Au P S (1933.35): calcd. C 43.45, H
2 2 70 52 4 4 4
3
P{ H} NMR (CDCl ): δ = 22.0 (s) ppm. IR (KBr): ν˜ = 2134
+
+
+
–1
+
[ν(CϵC)] cm . MS (LSIMS ): m/z (%) = 1223 (44), 1099 (7) [M +
+
+
+
H] , 1023 (11), 613 (35), 460 (100) [AuS(PPh
2
Me)] .
2
.59, S 6.62; found C 43.09, H 3.01, S 6.18. 13b: yellow solid
45 2 2 2
C H38Au P S
4
(1098.83): calcd. C 49.18, H 3.46, S 5.83; found C
8.79, H 3.09, S 5.51. 10e: orange solid (229 mg, 70%). H NMR
1
1
3
(239 mg, 58%). H NMR (CDCl ): δ = 7.36–7.31 (m, 20 H), 7.24–
7
3
1
1
3
.14 (m, 28 H), 2.44 (s, 8 H) ppm. P{ H} NMR (CDCl ): δ =
(
=
5
3
CDCl ): δ = 7.69–7.33 (m, 36 H), 1.39 (s, 6 H) ppm. IR (KBr): ν˜
3
–
1
+
–1
+
21.4 (s) ppm. IR (KBr): ν˜ = 2133 [ν(CϵC)] cm . MS (LSIMS ):
m/z (%) = 1845 (11), 1225 (69), 977 (100), 827 (90). C72
1961.17): calcd. C 44.06, H 2.86, S 6.53; found C 43.69, H 2.56, S
.05.
2130 [ν(CϵC)] cm . MS (LSIMS ): m/z (%) = 1235 (8), 809 (16),
As (1310.48): C, 50.36; H,
.20; S, 4.88. Found: C, 49.96; H, 2.95; S, 5.30.
4 4 4
H56Au P S
03 (28), 460 (100). Anal. C55
H42Au
2
2 2
S
(
6
Synthesis of [Au
2
{3,5-(S–CϵC) –C N)}L ] {L = PPh
Me (11b), AsPh (11e)}: To an ice-cooled solution of 3,5-
bis(1,2,3-thiadiazol-4-yl)-2,6-dimethylpyridine (5) (82 mg,
2
7
H
7
2
3
(11a),
PPh
2
3
Crystallographic Studies: Crystals suitable for X-ray diffraction
were obtained by slow diffusion of diethyl ether or hexane into
0
0
.3 mmol) in dry thf (15 mL) was added tBuOK (74 mg, solutions in dichloromethane. A summary of the fundamental crys-
.66 mmol). The mixture was stirred under an argon atmosphere
)] (267 mg, 0.52 mmol), [AuCl(AsPh )]
280 mg, 0.52 mmol) or [AuCl(PPh
tal and refinement data of compounds 7 and 11a are given in
Table 3. The crystals were mounted on glass fibre with inert oil
for 1 h, and then [AuCl(PPh
(
added. The mixture was stirred for a further 6 h. The solvent was
evaporated under vacuum to a volume of 5 mL, and diethyl ether
3
3
2
Me)] (225 mg, 0.52 mmol) was and centred on a Bruker-Siemens Smart CCD diffractometer. The
[85]
diffraction frames were integrated by using the SAINT package
and corrected for absorption with SADABS.[ The structures were
86]
solved by direct methods with SHELXS.[
87]
Full-matrix least-
(30 mL) was added to precipitate the corresponding product, which
[88]
was filtered off and washed with water. 11a: yellow solid (150 mg,
4
ppm. P{ H} NMR (CDCl ): δ = 37.5 (s) ppm. IR (KBr): ν˜ = riding model. Weighted R factors (R
2
squares refinement was carried out by using SHELXTL minim-
1
2
2 2
4%). H NMR (CDCl
3
): δ = 7.53–7.47 (m, 31 H), 2.54 (s, 6 H) izing ω(F
o
* – F
c
) . Hydrogen atoms were included by using a
) and all goodness-of-fit S
values are based on F ; conventional R factors (R) are based on F.
3 2 2 2
] . C47H37Au NP S (1135.63): In the case of complex 11a the diffraction data were weak, with
31
1
3
w
–1
+
2
133 [ν(CϵC)] cm . MS (LSIMS ): m/z (%) = 1409 (58), 1147
+
(14), 721 (27), 460 (100) [AuPPh
calcd. C 49.67, H 3.26, N 1.23, S 5.64; found C 49.58, H 2.89, N
mean I/σ(I) = 2.95 in the data set before averaging of equivalents,
and a Rint value of 10.05%. All non-hydrogen atoms were refined
1
1
.60, S 6.10. 11b: yellow solid (152 mg, 50%). H NMR (CDCl
44
3
):
1
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Eur. J. Inorg. Chem. 2009, 137–146