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Dalton Transactions
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Paper
Journal Name
Bromido[3-ethyl-4-(4-methoxyphenyl)-5-(6-methoxypyridin-3-yl)-
1-propyl-1,3-dihydro-2H-imidazol-2-ylidene]gold(I) (8c)
propyl-1,3-dihydro-2H-imidazol-2-ylidene]gold(I) (8g)
DOI: 10.1039/C9DT04824C
Colourless solid, 68 mg from 80 mg of hexafluorophosphate imidazo- Colourless solid, 88 mg from 80 mg of hexafluorophosphate
lium salt 7c (67% yield). 1H-NMR (CDCl3): δ = 0.85 (t, 3 H, J = 7.2 Hz), imidazolium salt 7g (87% yield). 1H-NMR (CDCl3): δ = 0.85 (t, 3 H, J =
1.31 (t, 3 H, J = 7.2 Hz), 1.75 (qt, 2 H, J = 7.4, 7.4 Hz), 3.81 (s, 3 H), 3.93 7.4 Hz), 1.32 (t, 3 H, J = 7.4 Hz), 1.77 (qt, 2 H, J = 7.4, 7.4 Hz), 3.94 (s,
(s, 3 H), 4.04-4.22 (m, 4 H), 6.74 (d, 1 H, J = 8.4 Hz), 6.89 (d, 2 H, J = 3 H), 4.04-4.27 (m, 4 H), 6.77 (d, 1 H, J = 8.8 Hz), 6.91-7.17 (m, 3 H),
8.8 Hz), 7.12 (d, 2 H, J = 8.8 Hz), 7.39 (dd, 1 H, J = 8.6, 2.4 Hz), 8.00 (d, 7.33-7.44 (m, 2 H), 8.00 (d, 1 H, J = 2.0 Hz). 13C-NMR (CDCl3): δ = 11.3,
1 H, J = 2.4 Hz). 13C-NMR (CDCl3): δ = 11.3, 17.0, 24.9, 44.4, 50.8, 53.9, 17.0, 24.9, 44.6, 50.9, 54.0, 111.6, 116.6, 117.0 (d, J = 21.0 Hz), 117.7
55.4, 111.4, 114.6, 117.1, 119.3, 128.1, 131.9 (two signals (d, J = 22.2 Hz), 126.5 (d, J = 3.1 Hz), 128.6, 129.4 (d, J = 8.0 Hz), 130.7,
overlapping), 140.3, 148.7, 160.5, 164.5, 173.5. FT-IR ATR (cm-1): 131.0 (d, J = 8.8 Hz), 140.4, 148.6, 162.7 (d, J = 249.2 Hz), 164.7, 174.3.
2961, 2933, 2873, 2837, 1645, 1607, 1593, 1573, 1514, 1489, 1367, FT-IR ATR (cm-1): 3060, 2970, 2950, 2930, 2871, 1650, 1612, 1595,
1284, 1248, 1172, 1007, 837, 550. ESI-MS m/z: 899.3559 (2M-Au- 1582, 1561, 1499, 1483, 1362, 1280, 1012, 880, 840, 681, 521. ESI-
Br2)+. Purity calculated by HPLC (peak area): 97.7 %.
MS m/z: 875.3107 (2M-Au-Br2)+, 1153.1925 (2M-Br)+. Purity
calculated by HPLC (peak area): 99.0 %.
Bromido[3-ethyl-4-phenyl-5-(6-methoxypyridin-3-yl)-1-propyl-1,3-
dihydro-2H-imidazol-2-ylidene]gold(I) (8d)
Bromido[3-ethyl-4-(4-fluorophenyl)-5-(6-methoxypyridin-3-yl)-1-
Colorless solid, 96 mg from 80 mg of hexafluorophosphate propyl-1,3-dihydro-2H-imidazol-2-ylidene]gold(I) (8h)
imidazolium salt 7d (94% yield). 1H-NMR (CDCl3): δ = 0.85 (t, 3 H, J = Colourless solid, 61 mg from 80 mg of hexafluorophosphate imi-
7.6 Hz), 1.31 (t, 3 H, J = 7.6 Hz), 1.76 (qt, 2 H, J = 7.6, 7.6 Hz), 3.92 (s, dazolium salt 7h (60% yield). 1H-NMR (CDCl3): δ = 0.85 (t, 3 H, J = 7.4
3 H), 4.05-4.25 (m, 4 H), 6.73 (d, 1 H, J = 8.4 Hz), 7.18-7.23 (m, 2 H), Hz), 1.31 (t, 3 H, J = 7.2 Hz), 1.76 (qt, 2 H, J = 7.6, 7.6 Hz), 3.93 (s, 3 H),
7.36-7.43 (m, 4 H), 8.01 (d, 1 H, J = 2.4 Hz). 13C-NMR (CDCl3): δ = 11.3, 4.04-4.23 (m, 4 H), 6.75 (d, 1 H, J = 8.6 Hz), 7.04-7.24 (m, 4 H), 7.39
17.0, 24.9, 44.5, 50.8, 53.9, 111.4, 116.9, 127.5, 128.2, 129.2, 129.8, (dd, 1 H, J = 8.6, 2.4 Hz), 7.99 (d, 1 H, J = 2.6 Hz). 13C-NMR (CDCl3): δ
130.6, 132.1, 140.4, 148.7, 164.5, 173.8. FT-IR ATR (cm-1): 3060, = 11.3, 17.0, 24.9, 44.5, 50.9, 53.9, 111.5, 116.5 (d, J = 21.7 Hz) (116.7
2964, 2930, 2874, 1632, 1605, 1589, 1561, 1458, 1461, 1363, 1284, overlapping with the signal corresponding to Cj of the pyridine),
1010, 800, 762, 702, 625, 552. ESI-MS m/z: 839.3297 (2M-Au-Br2)+. 123.5 (d, J = 3.8 Hz), 128.6, 131.0, 132.6 (d, J = 8.4 Hz), 140.3, 148.7,
Purity calculated by HPLC (peak area): 98.1 %.
163.4 (d, J = 251.0 Hz), 164.7, 174.0. FT-IR ATR (cm-1): 3056, 2970,
2874, 1596, 1560, 1514, 1491, 1348, 1285, 1223, 1159, 1013, 824,
519. ESI-MS m/z: 875.3105 (2M-Au-Br2)+, 1153.1920 (2M-Br)+. Purity
calculated by HPLC (peak area): 96.1 %.
Bromido[3-ethyl-4-(4-methylphenyl)-5-(6-methoxypyridin-3-yl)-1-
propyl-1,3-dihydro-2H-imidazol-2-ylidene]gold(I) (8e)
Colourless solid, 100 mg from 80 mg of hexafluorophosphate imida-
zolium salt 7e (98%). 1H-NMR (CDCl3): δ = 0.85 (t, 3 H, J = 7.4 Hz), 1.31
(t, 3 H, J = 7.4 Hz), 1.75 (qt, 2 H, J = 7.4 Hz), 2.35 (s, 3 H), 3.93 (s, 3 H),
4.04-4.23 (m, 4 H), 6.75 (d, 1 H, J = 8.8 Hz), 7.08 (d, 2 H, J = 8.0 Hz),
7.18 (d, 2 H, J = 8.0 Hz), 7.41 (dd, 1 H, J = 8.8, 2.6 Hz), 8.01 (d, 1 H, J =
2.2 Hz). 13C-NMR (CDCl3): δ = 11.3, 17.1, 21.5, 24.9, 44.4, 50.8, 53.9,
111.4, 117.1, 124.4, 128.0, 129.9, 130.5, 132.1, 139.9, 140.4, 148.7,
164.5, 173.6. FT-IR ATR (cm-1): 2964, 2945, 2872, 1642, 1608, 1593,
1560, 1515, 1488, 1455, 1364, 1283, 1246, 1009, 820, 497. ESI-MS
m/z: 867.3608 (2M-Au-Br2)+, 1145,2428 (2M-Br)+. Purity calculated
by HPLC (peak area): 98.0 %.
Biological methods
Cell lines
The acute myeloid leukemia (HL-60) and the chronic myeloid leuke-
mia (LAMA-84) cell lines were purchased from DSMZ - German
Collection of Microorganisms and Cell Cultures, Braunschweig,
Germany. MCF-7, MDA-MB-231 and HT-29 cell lines were purchased
from the cell line service (CLS, Eppelheim, Germany). The ovarian
carcinoma cell lines A2780 and A2780cis were kindly provided by the
Department of Gynecology, Medical University Innsbruck. The non-
cancerous lung fibroblast cell line SV 80 was kindly provided by the
Department of Hematology, Medical University Innsbruck. All cell
lines were grown in RPMI 1640 without phenol red (BioWhittaker,
Lonza, Walkersville, MD, USA), supplemented with L-glutamine (2
mM), penicillin (100 U/mL), streptomycin (100 µg/mL) and fetal
bovine serum (FBS; 10%; all from Invitrogen Corporation, Gibco,
Paisley, Scotland) at 37°C in a 5% CO2/95% air atmosphere and
fed/passaged twice weekly. LAMA-84 cells have been made resistant
to imatinib by treating with increasing concentrations of imatinib for
several weeks. To maintain resistance, A2780cis and LAMA-84 STI-
resistant cells were incubated every second week with 1 µM of
Cisplatin or 1.5 µM of Imatinib, respectively. The resistance of the
LAMA-84 cells is due to upregulation of drug transporters
(unpublished results), whereas A2780cis cells have an increased
ability to repair DNA damage and display cytogenetic
abnormalities.53
Bromido[3-ethyl-4-(2-fluorophenyl)-5-(6-methoxypyridin-3-yl)-1-
propyl-1,3-dihydro-2H-imidazol-2-ylidene]gold(I) (8f)
Colourless solid, 52 mg from 70 mg of hexafluorophosphate imida-
zolium salt 7f (59% yield). 1H-NMR (CDCl3): δ = 0.86 (t, 3 H, J = 7.6 Hz),
1.30 (t, 3 H, J = 7.6 Hz), 1.78 (qt, 2 H, J = 7.6, 7.6 Hz), 3.94 (s, 3 H),
4.05-4.13 (m, 4 H), 6.77 (d, 1 H, J = 8.6 Hz), 7.10-7.22 (m, 3 H), 7.39-
7.50 (m, 2 H), 8.02 (d, 1 H, J = 2.4 Hz). 13C-NMR (CDCl3): δ = 11.2, 16.8,
24.8, 44.9, 50.9, 54.0, 111.5, 115.3 (d, J = 15.5 Hz), 116.5 (d, J = 21.7
Hz), 116.7, 124.9 (d, J = 3.8 Hz), 125.9, 129.6, 132.6 (d, J = 8.0 Hz),
132.8 (d, J = 1.5 Hz), 140.2, 148.3, 160.7 (d, J = 249.2 Hz), 164.7, 174.6.
FT-IR ATR (cm-1): 3050, 3035, 2969, 2927, 2874, 1641, 1610, 1599,
1560, 1504, 1484, 1459, 1345, 1286, 1225, 1126, 1020, 826, 766, 549.
ESI-MS m/z: 875.3107 (2M-Au-Br2)+, 1153.1925 (2M-Br)+. Purity
calculated by HPLC (peak area): 98.2 %.
8 | J. Name., 2012, 00, 1-3
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