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6639
147.2 (s), 146.9 (s), 138.6 (s), 135.8 (s), 135.4 (s), 135.1
(s), 130.3 (s), 129.9 (s), 129.7 (s), 129.5 (s), 129.0 (s),
127.9 (s), 127.5 (s), 127.3 (s), 127.2 (s), 125.2 (s), 124.9
(s), 123.5 (s), 121.5 (s), 120.4 (s), 109.1 (s). MS (ESI)
(35 eV) m/z%: 681 (100) for [Ru(phen)2(itsz)].
RuC32H24N7SCl2: C, 51.5; H, 3.2; N, 13.15. Found: C,
51.7; H, 3.2; N, 14.9.
1H NMR (DMSO-d6): d = 10.19–10.08 (2H, m), 9.41
(1H, s), 8.87–8.83 (2H, m), 8.70 (1H, s, br), 8.54–8.52
(1H, m), 8.47–8.35 (3H, m), 8.30–8.23 (4H, m), 8.01
(2H, s, br, NH2), 7.91–7.86 (3H, m), 7.58 (1H, dd,
J = 8.2, 8.1 Hz), 7.51–7.46 (2H, m), 7.23 (1H, d,
J = 8.6 Hz), 6.95 (1H, d, J = 8.5 Hz). MS (ESI) (35 eV)
m/z%: 674 (100) for [Ru(phen)2(4-Cl-btsz)].
4.4.2. Ru2. Yield 40%. FTIR (KBr) cmꢀ1: 3410 (NH2),
3227 (N–H), 3040 (C–H), 1680 (C@O), 1611 (N–H)
and 1324 (C@S). kmax nm (MeOH): 219, 263, 398, and
470. Anal. Calcd for RuC29H24N8SOCl2: C, 49.4; H,
3.4; N, 15.9. Found: C, 49.7; H, 3.1; N, 15.2.
4.5.4. Ru6. Yield 38%. FTIR (KBr) cmꢀ1: 3395–3317
(NH2 and N–H), 1605 (N–H), 1300 (C@S). kmax nm
(MeOH): 205, 244, 294 397 and 458. Anal. Calcd for
RuC28H24N7SCl3: C, 48.2; H, 3.4; N, 14.05. Found: C,
48.3; H, 3.2; N, 14.9.
1H NMR (DMSO-d6): d = 9.77 (1H, s), 9.41 (1H, d),
8.83 (1H, d), 8.53 (1H, d), 8.48 (1H, d), 8.38–8.36 (2H,
d), 8.26 (1H, d), 8.09–7.98 (2H, tt), 7.89–7.78 (3H, m),
7.74 (1H, d), 7.63 (1H, t), 7.53 (1H, t), 7.49 (1H, d),
7.36 (2H, s, NH2), 7.13 (1H, t), 7.08–7.05 (2H, m),
6.81 (1H, t), 6.64 (1H, d). MS (ESI) (35 eV) m/z%: 633
(100) for [Ru(bpy)2(itsz)].
1H NMR (DMSO-d6): d = 9.98 (1H, m), 8.82–8.78 (2H,
m), 8.71 (1H, d, J = 5.6 Hz), 8.60 (1H, d, J = 8.0 Hz),
8.44 (1H, d, J = 8.0 Hz), 8.08–8.02 (3H, m), 7.78–7.72
(2H, m), 7.66–7.58 (2H, m), 7.48 (1H, d, J = 5.6 Hz),
7.32–7.23 (3H, m), 7.18–7.17 (3H, mt, J = 12.00 Hz),
6.97 (2H, d, J = 8.00 Hz) 6.22 (2H, s). MS (ESI)
(35 eV) m/z%: 626 (100) for [Ru(bpy)2(4-Cl-btsz)].
4.5. General procedure for preparing [Ru(S)2(r-btsz)]Cl2
(where S = 2,20-bipyridine/1,10-phenanthroline and r = 4-
OCH3 (Ru3), (Ru4); 4-Cl (Ru5), (Ru6); 2-Cl (Ru7), (Ru8);
2-F (Ru9), (Ru10) and btsz = 1-benzyl-thiosemicarbazone)
The compounds were prepared in a similar manner to
Ru1 with microcrystalline cis-bis(S)dichlororutheni-
um(II) [cis-Ru(S)2Cl2] and ligand (r-btsz), finally, they
were purified by column chromatography using silica
gel as stationary phase and chloroform–methanol as
eluent.
4.5.5. Ru7. Yield 37%. FTIR (KBr) cmꢀ1: 3392–3312
(NH2 and N–H), 1608 (N–H), 1309 (C@S). kmax nm
(MeOH): 206, 223, 265, 402 and 455. Anal. Calcd for
RuC32H24N7SCl3: C, 51.5; H, 3.2; N, 13.15. Found: C,
51.7; H, 3.2; N, 13.1.
1H NMR (DMSO-d6): d = 9.88 (1H, d, J = 5.39 Hz),
8.79–8.73 (4H, m), 8.65–8.61 (3H, m), 8.17–8.13 (3H,
m), 7.98–7.83 (5H, m), 7.78 (1H, d, J = 5.2 Hz), 7.52
(1H, d, J = 5.0 Hz), 7.39 (2H, t, J = 13.0 Hz), 7.26–
7.21 (3H, m), 6.83 (1H, s).
4.5.1. Ru3. Yield 47%. FTIR (KBr) cmꢀ1: 3401–3313
(NH2 and N–H), 1601 (N–H), 1305 (C@S). kmax nm
(MeOH): 205, 222, 265, 315, 396 and 440. Anal. Calcd
for RuC33H27N7SOCl2: C, 53.4; H, 3.6; N, 13.2. Found:
C, 53.2; H, 3.3; N, 13.0.
13C NMR (DMSO-d6): d = 181.95 (s), 154.87 (s), 153.63
(s), 152.73 (d), 148.99 (s), 148.88 (s), 148.74 (s), 148.31
(s), 139.70 (s), 134.57 (d), 134.37 (s), 134.19 (s), 133.17
(s), 130.05 (s), 129.79 (s), 128.81 (s), 128.48 (s), 126.30
(s), 125.95 (s), 125.36 (s), 125.06 (s), 62.86 (s). MS
(ESI) (35 eV) m/z%: 674 (100) for [Ru(phen)2(2-Cl-
btsz)].
1H NMR (DMSO-d6): d = 10.01 (1H, d), 8.90 (1H, d),
8.83 (2H, t), 8.65 (1H, d), 8.48 (1H, d), 8.36–8.18 (6H,
m), 8.15–8.09 (2H, m), 7.92 (1H, d), 7.80–7.74 (2H, m)
7.67–7.63 (1H, m), 7.48–7045 (1H, m), 6.91 (2H, s, br,
NH2), 6.74 (2H, d), 6.14 (1H, s), 3.69 (3H, s, OCH3).
MS (ESI) (35 eV) m/z%: 670 (100) for [Ru(phen)2(4-
MeO-btsz)].
4.5.6. Ru8. Yield 40%. FTIR (KBr) cmꢀ1: 3397–3319
(NH2 and N–H), 1611 (N–H), 1308 (C@S). kmax nm
(MeOH): 211, 244, 294, 340, 400 and 485. Anal. Calcd
for RuC28H24N7SCl3: C, 48.2; H, 3.4; N, 14.05. Found:
C, 48.7; H, 3.3; N, 14.9.
4.5.2. Ru4. Yield 43%. FTIR (KBr) cmꢀ1: 3418–3310
(NH2 and N–H), 1603 (N–H), 1303 (C@S). kmax nm
(MeOH): 208, 241, 294, 315, 397 and 460. Anal. Calcd
for RuC29H27N7SOCl2: C, 50.2; H, 3.9; N, 14.1. Found:
C, 50.7; H, 3.5; N, 14.9.
1H NMR (DMSO-d6): d = 10.02 (1H, d), 8.73–8.72 (1H,
d), 8.64–8.39 (5H, m), 8.10–8.04 (3H, m), 8.01–7.97 (1H,
m), 7.86–7.68 (6H, tm), 7.47 (2H, d), 7.39–6.89 (5H, m).
MS (ESI) (35 eV) m/z%: 626 (100) for [Ru(bpy)2(2-Cl-
btsz)].
1H NMR (DMSO-d6): d = 10 (1H, d), 8.91 (1H, d),
8.73–8.40 (5H, m), 8.13–7.97 (2H, m), 7.83–7.52
(3H, m), 7.45–7.33 (2H, m), 7.22–7.16 (1H, m),
7.10–6.98 (2H, m), 6.93–6.71 (3H, m), 6.60 (2H, s,
br, NH2), 6.35–6.12 (2H, m), 3.73 (3H, s, OCH3).
MS (ESI) (35 eV) m/z%: 622 (100) for [Ru(bpy)2(4-
MeO-btsz)].
4.5.7. Ru9. Yield 42%. FTIR (KBr) cmꢀ1: 3397–3311
(NH2 and N–H), 1611 (N–H), 1308 (C@S). kmax nm
(MeOH): 211, 244, 294 340, 400 and 485. Anal. Calcd
for RuC32H24N7SFCl2: C, 52.7; H, 3.3; N, 13.4. Found:
C, 52.5; H, 3.1; N, 13.1. MS (ESI) (35 eV) m/z%: 659
(100) for [Ru(phen)2(2-F-btsz)].
4.5.3. Ru5. Yield 40%. FTIR (KBr) cmꢀ1: 3398–3312
(NH2 and N–H), 1601 (N–H), 1305 (C@S). kmax nm
(MeOH): 221, 266, 399 and 467. Anal. Calcd for