J = 7.2 Hz), 7.00 (2H, d, J = 7.8 Hz), 2.28 (3H, s); m/z 1540
(53%), 650 ([M]+, 8%), 503 ([AuAsPh3]+, 100%) (LSIMS+). L =
PPh2Me (7c), yellow solid (85%). Found: C, 48.16; H, 3.87; S,
6.12. C22H20AuPS requires C, 48.53; H, 3.68; S, 5.88; m/cm−1:
2145 (C≡C) (KBr); dH (CDCl3): 7.60–7.40 (10H, m), 7.26 (2H,
d, J = 8.1 Hz), 7.00 (2H, d, J = 8.1 Hz), 2.30 (3H, s), 2.13 (3H,
d, J = 9.9 Hz); dP (CDCl3): 22.6 (s); m/z 544 ([M]+, 8%), 397
([AuPPh2Me]+, 100%) (LSIMS+).
H, 2.71; S, 10.25. C24H18AuPS2 requires C, 48.16; H, 3.03; S, 10.72;
m/cm−1: 2138 (C≡C) (KBr); dH (CDCl3): 7.61–7.48 (15H, m), 7.21–
7.08 (3H, m); dP (CDCl3): 37.7 (s); m/z 1409 (70%), 721 (21%), 598
([M]+, 13%) (LSIMS+). L = AsPh3 (9b), brown solid (96%). Found:
C, 44.66; H, 2.55; S, 9.64. C24H18AsAuS2 requires C, 44.88; H, 2.81;
S, 9.99; m/cm−1: 2139 (C≡C) (KBr); dH (CDCl3): 7.60–7.40 (m);
m/z 1541 (81%), 809 (75%), 642 ([M]+, 37%), 503 ([AuAsPh3]+,
100%) (LSIMS+). L = PPh2Me (9c), white solid (92%). Found: C,
42.17; H, 2.65; S, 11.72. C19H16AuPS2 requires C, 42.54; H, 3.00;
S, 11.96; m/cm−1: 2139 (C≡C) (KBr); dH (CDCl3): 7.68–7.50 (10H,
m), 7.20–7.08 (3H, m), 2.17 (3H, d, J = 10.5 Hz); dP (CDCl3): 22.0
(s); m/z 1223 (74%), 536 ([M]+, 14%), 397 ([AuPPh2Me]+, 100%)
(LSIMS+). L = PPhMe2 (9d), brown solid (47%). Found: C, 35.10;
H, 2.56; S, 14.00. C14H14AuPS2 requires C, 35.44; H, 2.95; S, 13.50;
m/cm−1: 2140 (C≡C) (KBr); dH (CDCl3): 7.73–7.50 (5H, m), 7.17–
7.06 (3H, m), 1.83 (6H, d, J = 10.5 Hz); dP (CDCl3): 8.9 (s); m/z
474 ([M]+, 35%), 335 ([AuPPhMe2]+, 100%) (LSIMS+). L = PMe3
(9e), pale brown solid (77%). Found: C, 25.79; H, 2.45; S, 15.09.
C9H12AuPS2 requires C, 26.19; H, 2.93; S, 15.56; m/cm−1: 2141
(C≡C) (KBr); dH (CDCl3): 7.23–7.04 (3H, m), 1.58 (9H, d, J =
0.8 Hz); dP (CDCl3): −3.5 (s); m/z 851 ([S(AuPMe3)2]+, 100%), 685
([M + AuPMe3]+, 5%), 412 ([M]+, 7%), 349 (45%) (LSIMS+).
Synthesis of [Au(2-C4H3S–C≡C–S)L], L = PPh3 (8a), AsPh3
(8b), PPh2Me (8c), PPhMe2 (8d), PMe3 (8e). To an ice-cooled
solution of 4-(2-thienyl)-1,2,3-thiadiazole 3 (84 mg, 0.5 mmol) in
dry THF (25 ml) was added tBuOK (62 mg, 0.55 mmol), for R =
PPh2Me was added LiN(SiMe3)2 1 M in hexane (0.5 ml, 0.5 mmol).
The mixture was stirred, under an argon atmosphere, for 1 h and
then [AuCl(PPh3)] (198 mg, 0.4 mmol), [AuCl(AsPh3)] (215 mg,
0.4 mmol), [AuCl(PPh2Me)] (216 mg, 0.5 mmol), [AuCl(PPhMe2)]
(148 mg, 0.4 mmol) or [AuCl(PMe3)] (123 mg, 0.4 mmol) were
added. The mixture was stirred for a further 6 h. The resulting
solution was then filtered through Celite to eliminate KCl. The
solvent was evaporated under vacuum to 5 ml and diethyl ether
(20 ml) was added to precipitate the corresponding product, which
was filtered off. L = PPh3 (8a), pale brown solid (71%). Found: C,
47.84; H, 2.68; S, 10.88. C24H18AuPS2 requires C, 48.16; H, 3.03;
S, 10.72; m/cm−1: 2125 (C≡C) (KBr); dH (CDCl3): 7.55–7.44 (15H,
m), 7.03–7.00 (2H, m), 6.86 (1H, dd, J = 5.1, 3.6 Hz); dP (CDCl3):
37.7 (s); m/z 721 (34%), 598 ([M]+, 21%), 459 ([AuPPh3]+, 100%)
(LSIMS+). L = AsPh3 (8b), yellow solid (72%). Found: C, 44.68;
H, 2.42; S, 10.46. C24H18AsAuS2 requires C, 44.88; H, 2.81; S,
9.99; m/cm−1: 2124 (C≡C) (KBr); dH (CDCl3): 7.52–7.44 (15H, m),
7.04–6.85 (3H, m); m/z 642 ([M]+, 18%), 503 ([AuAsPh3]+, 57%),
154 (100%) (LSIMS+). L = PPh2Me (8c), pale brown solid (55%).
Found: C, 42.32; H, 2.99; S, 11.63. C19H16AuPS2 requires C, 42.54;
H, 3.00; S, 11.96; m/cm−1: 2126 (C≡C) (KBr); dH (CDCl3): 7.64–
7.43 (10H, m), 7.02–6.83 (3H, m), 2.11 (3H, m); dP (CDCl3): 21.6
(s); m/z 597 (40%), 536 ([M]+, 12%), 397 ([AuPPh2Me]+, 100%)
(LSIMS+). L = PPhMe2 (8d), orange solid (20%). Found: C, 35.10;
H, 2.58; S, 14.00. C14H14AuPS2 requires C, 35.44; H, 2.95; S, 13.50;
m/cm−1: 2124 (C≡C) (KBr); dH (CDCl3): 7.74–7.48 (5H, m), 7.22–
6.87 (3H, m), 1.81 (6H, d, J = 10.2 Hz); dP (CDCl3): 9.6 (s);
m/z 425 (75%), 475 ([M + H]+, 5%), 643 (57%) (LSIMS+). L =
PMe3 (8e), yellow solid (25%). Found: C, 26.59; H, 2.76; S, 15.31.
C9H12AuPS2 requires C, 26.19; H, 2.93; S, 15.56; m/cm−1: 2123
(C≡C) (KBr); dH (CDCl3): 7.03–6.84 (3H, m), 1.58 (9H, d, J =
12.0 Hz); dP CDCl3): −3.4 (s); m/z 461 (42%), 412 ([M]+, 42%),
401 ([M − C]+, 69%), 349 ([Au(PMe3)2]+, 100%) (LSIMS+).
Synthesis of [Au(2-C15H13C≡C–S)L], L = PPh3 (10a), AsPh3
(10b), PPh2Me (10c), PMe3 (10e),. To an ice-cooled solution of 4-
(9,9-dimethylfluoren-2-yl)-1,2,3-thiadiazole 5 (133 mg, 0.5 mmol)
t
in dry THF (25 ml) was added BuOK (62 mg, 0.55 mmol). The
mixture was stirred, under an argon atmosphere, for 1 h and
then [AuCl(PPh3)] (198 mg, 0.4 mmol), [AuCl(AsPh3)] (215 mg,
0.4 mmol), [AuCl(PPh2Me)] (173 mg, 0.4 mmol) or [AuCl(PMe3)]
(123 mg, 0.4 mmol) were added. The mixture was stirred for
a further 6 h. The resulting solution was then filtered through
Celite to eliminate KCl. The solvent was evaporated under
vacuum to 5 ml and hexane (20 ml) was added to precipitate
the corresponding product, which was filtered off. L = PPh3 (10a),
yellow solid (80%). Found: C, 58.96; H, 3.82; S, 4.08. C35H28AuPS
requires C, 59.32; H, 3.95; S, 4.52; m/cm−1: 2132 (C≡C) (KBr); dH
(CDCl3): 7.68–7.30 (22H, m), 1.45 (6H, s); dP (CDCl3): 37.5 (s);
m/z 721 ([Au(PPh3)2]+, 100%), 708 ([M]+, 19%) (LSIMS+). L =
AsPh3 (10b), pale brown solid (74%). Found: C, 55.46; H, 3.44; S,
3.90. C35H28AsAuS requires C, 55.85; H, 3.72; S, 4.26; m/cm−1: 2132
(C≡C) (KBr); dH (CDCl3): 7.62–7.45 (22H, m), 1.41 (6H, s); m/z
1541 (12%), 809 (30%), 752 ([M]+, 18%), 503 ([AuAsPh3]+, 100%)
(LSIMS+). L = PPh2Me (10c), yellow solid (98%). Found: C, 55.35;
H, 3.82; S, 4.58. C30H26AuPS requires C, 55.73; H, 4.02; S, 4.95;
m/cm−1: 2132 (C≡C) (KBr); dH (CDCl3): 7.68–7.30 (17H, m), 2.17
(3H, d, J = 9.3 Hz), 1.46 (6H, s); dP (CDCl3): 21.9 (s); m/z 1223
(25%), 646 ([M]+, 6%), 397 ([AuPPh2Me]+, 100%) (LSIMS+). L =
PMe3 (10e), pale brown solid (87%). Found: C, 45.63; H, 3.85;
S, 5.79. C20H22AuPS requires C, 45.98; H, 4.25; S, 6.14; m/cm−1:
2131 (C≡C) (KBr); dH (CDCl3): 7.67–7.28 (7H, m), 1.60 (9H,
d, J = 12.6 Hz), 1.44 (6H, m); dP (CDCl3): −3.5 (s); m/z 851
([S(AuPMe3)2]+, 50%), 522 ([M]+, 10%), 349 ([Au(PMe3)2]+, 100%)
(LSIMS+).
Synthesis of [Au(3-C4H3S–C≡C–S)L], L = PPh3 (9a), AsPh3
(9b), PPh2Me (9c), PPhMe2 (9d), PMe3 (9e),. To an ice-cooled
solution of 4-(3-thienyl)-1,2,3-thiadiazole 4 (84 mg, 0.50 mmol)
t
in dry THF (25 ml) was added BuOK (62 mg, 0.55 mmol).
The mixture was stirred, under argon atmosphere, for 1 h and
then [AuCl(PPh3)] (198 mg, 0.4 mmol), [AuCl(AsPh3)] (215 mg,
0.4 mmol), [AuCl(PPh2Me)] (173 mg, 0.5 mmol), [AuCl(PPhMe2)]
(148 mg, 0.4 mmol) or [AuCl(PMe3)] (123 mg, 0.4 mmol) were
added. The mixture was stirred for a further 6 h. The resulting
solution was then filtered through Celite to eliminate KCl. The
solvent was evaporated under vacuum to 5 ml and hexane (20 ml)
was added to precipitate the corresponding product, which was
filtered off. L = PPh3 (9a), orange solid (97%). Found: C, 47.88;
Synthesis of PPN[Au(p-CH3–C6H4–C≡C–S)(C6F5)] (11).
Compound 11 was prepared by a procedure similar to 7 using
PPN[AuCl(C6F5)] (375 mg, 0.4 mmol). White solid (66%). Found:
C, 57.99; H, 3.19; N, 1.20; S, 2.59. C51H37AuF5NP2S requires C,
58.31; H, 3.52; N, 1.33; S, 3.05; m/cm−1: 2143 (C≡C) (KBr); dH
This journal is
The Royal Society of Chemistry 2007
Dalton Trans., 2007, 5329–5338 | 5335
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