T. Stringer et al. / Inorganic Chemistry Communications 14 (2011) 956–960
959
°C. FT-IR (KBr,cm-1): 1600 (C=N), 860 (C=S). 1H NMR (300 MHz, DMSO–d6): δ
(ppm) = 7.76 (m, 6H, CH (benzaldehyde)), 7.92 (s, 4H, Ph), 8.24 (m, 4H,
benzaldehyde), 8.52 (s, 2H, CH=N), 10.38 (s, 2H, -CNHC-); 12.06 (2H, s, -NHN=).
13C{1H} NMR (100 MHz, DMSO–d6): δ (ppm) 125.92, 128.05-134.43 (benzalde-
hyde), 136.62, 143.30 (C=N), 176.43 (C=S). Elemental analysis (%): Calc. for
Table 1
IC50 values obtained for complexes (1–4) as well as their corresponding free ligands
(L1 and L2) against WHCO1 cells.
a
Compound
IC50 (μM)
95% Confidence Interval
C
22H20N6S2: C, 61.08; H, 4.66; N, 19.43; S, 14.38. Found: C, 60.73; H, 5.17; N, 19.67;
S, 14.28. ESI-MS: m/z 455 (100%, [M+Na]+).
L1
L2
1
2
3
N200
0.21
81.13
N200
N200
8.96
not applicable
0.11–0.38
69.87–94.21
not applicable
not applicable
1.26–63.78
[34] M.A. Bennett, A.K. Smith, J. Chem. Soc. Dalton Trans. 2 (1974) 233–241.
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1873–1882.
[36] General Procedure for the synthesis of 1–4: Complexes were prepared by reaction
of [Ru(η6-arene)(μ-Cl)Cl]2 and L1 (1:2) or L2 (1:1) in CH2Cl2 or MeOH. All
reactions were carried out by stirring the contents at ambient temperature for 16–
24 hours. Soluble products were precipitated using diethyl ether after solvent
reduction. The solids were obtained as red or orange solids. Complex 1: Yield =
0.155 g (62%). M.p.: 177–181 °C. FT-IR (KBr,cm-1) 1618 (C=N), 875 (C=S). 1H
NMR (400 MHz, CDCl3): δ (ppm) = 1.07 (d, 3H, CH3 (iPr), 3JH-H = 6.81), 1.13 (d,
3H, CH3 (iPr), 3JH-H = 6.94), 2.05 (s, 3H, CH3), 2.61 (m, 1H, CH (methine)), 4.64 (d,
1H, CH (p-cymene), 3JH-H = 5.72), 4.80 (d, 1H, CH (p-cymene), 3JH-H = 5.82), 4.88
4
a
Drug concentration required for 50% inhibition of cell viability.
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(d, 1H, CH (p-cymene), JH-H = 5.79), 5.41 (d,1H, CH (p-cymene), 3JH-H = 5.79),
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C
18H23Cl2N3RuS.MeOH: C, 44.10; H, 5.26; N, 8.12; S, 6.20. Found: C, 44.22; H, 4.82;
N, 7.92; S, 6.07. ESI-MS: m/z 414 (100%, [M-HCl-Cl]+). Complex 2: Yield = 0.225 g
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3
COOH), 2.37 (t, 2H, CH2CH2CH2COOH, JH-H = 7.14), 2.44 (t, 2H, CH2CH2CH2-
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3
3
3
3
3
3
3
(benzaldehyde)), 8.24 (d, 2H, CH (benzaldehyde), JH-H = 5.86), 8.81 (s, 1H,
CH=N). 13C{1H} NMR (100 MHz, CD3OD): δ (ppm) = 24.36, 32.13, 32.48, 81.25-
106.25 (arene), 128.63-133.47 (benzaldehyde), 162.35 (C=N), 174.98 (C=O),
177.82 (C=S). Elemental analysis (%): Calc. for C18H21Cl2N3O2RuS: C, 41.94; H,
4.11; N, 8.15; S, 6.22. Found: C, 41.52; H, 4.13; N, 7.86; S, 5.91. ESI-MS: m/z 444
(100%, [M-HCl-Cl]+). Complex 3: Yield = 0.187 g (68%). M.p.: decomposes at 224
°C. FT-IR (KBR, cm-1): 1614 (C=N), 869 (C=S). 1H NMR (400 MHz, CDCl3): δ
(ppm) = 1.09 (d, 6H, CH3 (iPr), 3JH-H = 6.74); 1.15 (d, 6H, CH3 (iPr), 3JH-H = 6.82),
2.07 (s, 6H, CH3), 2.64 (m, 2H, CH (methine)), 4.69 (m, 2H, CH (p-cymene)), 4.82
(d, 2H, CH (p-cymene), 3JH-H = 5.39), 4.92 (d, 2H, CH (p-cymene), 3JH-H = 4.86),
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3
5.41 (d, 2H, CH (p-cymene), JH-H = 5.67), 7.58 (m, 12H, CH (benzene), CH
(benzaldehyde), NNH), 8.19 (d, 4H, CH (benzaldehyde), 3JH-H = 6.44), 9.04 (s, 2H,
CH=N), 10.66 (s, 2H, CNHC-). 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) = 18.65,
21.40, 23.14, 30.76, 81.91-88.88 (p-cymene), 103.97, 124.35 (benzene), 124.48,
128.90-133.49 (benzaldehyde), 135.28, 161.45 (C=N), 175.97 (C=S). Elemental
analysis (%): Calc. for C42H48Cl4N6Ru2S2·½CH2Cl2: C, 46.94; H, 4.54; N, 7.73; S,
5.90. Found: C, 46.54; H, 4.69; N, 7.44; S, 5.78. ESI-MS: m/z 945 (85%, [M-4HCl-H+
2Na]+). Complex 4: Yield = 0.179 g (89%). M.p. decomposes at 158 °C. FT-IR
(KBr, cm-1): 1727 (C=O), 1600 (C=N), 845 (C=S). 1H NMR (400 MHz, CD3OD): δ
(ppm) = 1.81 (qn, 4H, CH2CH2CH2COOH); 2.30 (m, 8H, CH2CH2CH2COOH); 4.99
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3
3
(d, 2H, CH (arene), JH-H = 5.73), 5.04 (d, 2H, CH (arene), JH-H = 6.14), 5.13 (t,
2H, CH (arene), 3JH-H = 5.63), 5.28 (t, 2H, CH (arene), 3JH-H = 6.06), 5.40 (t, 2H, CH
3
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[33] Procedure for the synthesis of L2: Benzene-1,4-dithiosemicarbazide (0.140 g,
0.544 mmol) was added to warm MeOH (25 cm3). Benzaldehyde (0.11 cm3) was
added and the suspension refluxed for 24 hours yielding a white solid. The
product (L2) was filtered, washed with MeOH and diethyl ether and then dried in
vacuo. L2 was obtained as a white powder. Yield = 0.215 g (91%). M.p.: 262–265
[47] The compounds were evaluated against the WHCO1 cancer cell line. These cells
were derived from biopsies of primary oesophageal squamous cell carcinomas