K.J. Kilpin et al. / Polyhedron 26 (2007) 434–447
445
59 mg (35%) of white microcrystals. Anal. Calc. for
C28H28N3O4S2Au: C, 46.0; H, 3.9; N, 5.8. Found: C,
45.9; H, 4.0; N, 5.8%. M.p. 215–219 ꢁC (dec.). IR: m(SO2,
asym) 1280 cmꢀ1; m(SO2, sym) 1139 cmꢀ1. ESI-MS: cone
voltage 20 V; m/z 791 (100%, [M+Me3NH]+), 732 (95%,
[M+H]+), 754 (80%, [M+Na]+), 1485 (35%, [2M+Na]+),
1463 (30%, [2M+H]+). Cone voltage 60 V: m/z 732
(100%, [M+H]+), 754 (95%, [M+Na]+), 1485 (40%,
20 V; m/z 754 (100%, [M+Na]+), 1485 (25%, [2M+Na]+),
791 (20%, [M+Me3NH]+), 732 (15%, [M+H]+). Cone
voltage 60 V: m/z 754 (100%, [M+Na]+), 732 (50%,
1
[M+H]+), 1485 (20%, [2M+Na]+). H NMR: d 2.30 (s,
3H), 2.41 (s, 3H), 2.94 (s, 3H), 3.20 (d, 2H), 3.27 (d,
2H), 7.13–7.43 (m, 7H), 7.55 (s 1H), 7.77–7.86 (m, 5H),
8.03 (t, 1H), 9.45 (d, 1H). 13C–{1H} NMR: d 21.56
(CH3), 21.74 (2 · CH3), 51.1 (CH2), 57.7 (CH2), 119.6–
165.1 (aryl C).
1
[2M+Na]+). H NMR: d 2.37 (s, 3H), 2.38 (s, 3H), 3.10
(m, 2H), 3.51 (m, 2H), 4.01 (d, 1H), 4.55 (d, 1H), 6.80 (t,
1H), 7.06–7.33 (m, 9H), 7.42 (t, 1H), 7.63 (d, 1H), 7.75
(d, 2H), 7.94 (t, 1H), 9.16 (d, 1H). 13C–{1H} NMR: d
21.4 (CH3), 21.5 (CH3), 47.9 (CH2), 51.0 (CH2), 56.6
(CH2), 123.2–156.0 (aryl C).
4.14. Synthesis of (damp)Au{N(SO2Tol)C2H4N(SO2Tol)}
(25)
The complex (damp)AuCl2 (8) (75 mg, 0.19 mmol) and
bis(sulfonamide) (16) (83 mg, 0.26 mmol) were mixed in
refluxing methanol (30 mL), producing a pale yellow solu-
tion. Aqueous trimethylamine (2 mL, excess) was added
and the mixture refluxed for 5 min. Water (75 mL) was
added, resulting in the deposition of pale yellow microcrys-
tals which were cooled, filtered and washed with water
(2 · 10 mL) and diethyl ether (10 mL) and then dried under
vacuum to give 115 mg (88%) of 25. Anal. Calc. for
C25H30N3O4S2Au: C, 43.0; H, 4.3; N, 6.0. Found: C,
42.9; H, 4.3; N, 5.9%. M.p. 184–187 ꢁC (dec.). IR: m(SO2,
asym) 1276 cmꢀ1; m(SO2, sym) 1138 cmꢀ1. ESI-MS: cone
voltage 20 V; m/z 719 (100%, [M+Na]+), 1415 (35%,
[2M+Na]+). Cone voltage 60 V: m/z 719 (100%,
4.12. Synthesis of (2-anp)Au{N(SO2Tol)C2H4N-
(SO2Tol)} (23)
The complex (2-anp)AuCl2 (6) (100 mg, 0.23 mmol) and
bis(sulfonamide) (16) (100 mg, 0.28 mmol) were added to
refluxing methanol (30 mL). While stirring, aqueous tri-
methylamine (2 mL, excess) was added and the solution
was refluxed for a further 15 min. Water (50 mL) was
added resulting in the formation of a pale yellow precipi-
tate. After cooling, the solid was filtered and washed with
water (2 · 10 mL) and diethyl ether (10 mL), and dried
under vacuum to give 111 mg (54%) of yellow product.
Anal. Calc. for C27H27N4O4S2Au: C, 44.3; H, 3.7; N, 7.7.
Found: C, 44.1; H, 3.8; N, 7.8%. M.p. 244–246 ꢁC
(decomp). IR: m(SO2, asym) 1276 cmꢀ1, m(SO2, sym)
1140 cmꢀ1; m(NH) 3295 cmꢀ1. ESI-MS: cone voltage
20 V; m/z 755 (100%, [M+Na]+), 1487 (20%, [2M+Na]+),
1121 (20%, [3M+2Na]2+). Cone voltage 60 V: m/z 755
1
[M+Na]+), 1415 (30%, [2M+Na]+). H NMR: d 2.40 (s,
6H), 3.13 (m, 2H), 3.18 (m, 2H), 3.40 (s, 6H), 4.34 (s,
2H), 6.97 (t, 1H), 7.12 (d, 1H), 7.17–7.25 (m, 5H), 7.38
(d, 1H), 7.65 (d, 2H), 7.73 (d, 2H). 13C–{1H} NMR: d
21.5 (CH3), 21.5 (CH3), 52.0 (CH2), 52.5 (NCH3), 58.1
(CH2), 77.1 (CH2), 123.0–147.4 (aryl C).
1
(100%, [M+Na]+), 1487 (25%, [2M+Na]+). H NMR: d
2.44 (s, 6H), 3.29 (m, 2H), 3.62 (m, 2H), 6.69 (t, 1H),
6.76 (t, 1H), 7.03 (m, 2H), 7.22–7.35 (m, 4H), 7.45 (d,
1H), 7.63 (m, 3H), 7.42 (t, 1H), 7.90 (d, 2H), 8.73 (d,
1H), 8.83 (s, NH). Due to the insolubility of this compound
in common deuterated NMR solvents [(CD3)2SO, D2O,
CDCl3], satisfactory 13C NMR spectra could not be
acquired.
4.15. Synthesis of (2-bp)Au{N(COMe)C6H4NH-
(COMe)}Cl (28)
The complex (2-bp)AuCl2 (5) (200 mg, 0.46 mmol), 1,2-
diacetamidobenzene (9) (90 mg, 0.46 mmol) and silver(I)
oxide (400 mg, excess) were added to dichloromethane
(50 mL) and refluxed with stirring for 2 h. The solution
was then filtered and the filtrate evaporated to dryness
under reduced pressure. The resulting yellow crystals were
dissolved in the minimum amount of dichloromethane
and filtered through an alumina column. Slow addition
of diethyl ether gave a pale yellow precipitate which was
subsequently filtered and washed with diethyl ether
4.13. Synthesis of (tolpy)Au{N(SO2Tol)C2H4N(SO2Tol)}
(24)
The complex (tolpy)AuCl2 (7) (100 mg, 23 mmol) and
bis(sulfonamide) (16) (100 mg, 0.23 mmol) were stirred
in refluxing methanol (30 mL) and aqueous trimethyla-
mine (2 mL, excess) was added, and the solution refluxed
for 5 min. Water (50 mL) was added and the mixture
cooled. The resulting pale yellow precipitate was filtered
and washed with water (2 · 10 mL) and diethyl ether
(10 mL) and dried under vacuum to give 135 mg (80%)
of pale yellow microcrystals. Anal. Calc. for C28H28N3O4-
S2Au: C, 46.0; H, 3.9; N, 5.8. Found: C, 45.7; H, 3.9;
N, 5.8%. M.p. 186–188 ꢁC (dec.). IR: m(SO2, asym)
1303 cmꢀ1; m(SO2, sym) 1138 cmꢀ1. ESI-MS: cone voltage
1
(10 mL) and water (2 · 10 mL). H NMR of the sample
showed it to be a mixture of mainly 28 plus the metalla-
cyclic complex 10. X-ray quality crystals of 28 were grown
by vapour diffusion of diethyl ether into a dichlorometh-
ane solution of the mixture at room temperature. M.p.
180–182 ꢁC (dec.). Anal. Calc. for C22H21N3O2AuCl: C,
44.6; H, 3.5; N, 7.10. Found: C, 42.1; H, 3.4; N, 6.1%.
Anal. Calc. for C22H21N3O2AuCl Æ 2H2O: C, 42.1; H,
3.4; N, 6.7%. IR: m(N–H) 3303 cmꢀ1, m(C@O) region
1693, 1611 cmꢀ1. ESI-MS: cone voltage 20 V; m/z 614