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Transition Met Chem (2010) 35:877–883
General preparation of the azoimine ligands (L)
(CDCl3): d 7.50 (d, 1H, H5), 7.35 (d, 2H, H1, H3),
7.15 (m, 6H, H7, H9, H10, H11, H12, H13), 6.95 (t, 1H,
H6), 6.80 (d, 2H, H2, H4), 6.22 (d, 1H, H8), 2.50
(s, 3H, COCH3). UV–Vis in acetonitrile: kmax(nm)
(emax, M-1 cm-1): 351 (8.92 9 104), 294 (5.32 9 104),
243 (6.98 9 104). C21H16BrN3OS, Found: C, 57.5; H, 3.8;
N, 9.4%. Calculated: C, 57.5; H, 3.7; N, 9.6%.
A solution of 2-thiophenylaniline (1.86 g, 20 mmol), tri-
ethylamine (2.4 g, 24 mmol) and the appropriate hyd-
razonyl chloride (20 mmol) in 15.0 cm3 ethanol was
refluxed for 2 h. Cooling the solution produced a yellow
solid that was recrystallized from ethanol.
1-(4-Nitrophenylhydrazono)-1-{[2-(phenylthio)
1-(Phenylhydrazono)-1-{[2-(phenylthio)
phenyl]imino}acetone (L5)
phenyl]imino}acetone (L1)
Yield = 4.05 g, 56%. M.p = 107–109 ꢁC. I.r. (KBr, cm-1):
mN=N = 1,496, mC=N = 1,601, mC=O = 1,668. 1H NMR
(CDCl3): d 7.55 (d, 1H,H5), 7.30 (d, 2H, H1, H3), 7.20
(m, 6H, H7, H9, H10, H11, H12, H13), 7.00 (d, 2H, H2, H4),
6.95 (t, 1H, H6), 6.91 (t, 1H, HY), 6.25 (d, 1H, H8), 2.55
Yield = 4.0 g, 49%. M.p. = 148–150 ꢁC. I.r. (KBr,
cm-1): mN=N = 1,500, mC=N = 1,605, mC=O = 1,673. 1H
NMR (CDCl3,): d 8.15 (d, 2H, H1, H3), 7.50 (d, 1H, H5),
7.20 (d, 2H, H2, H4), 7.05 (m, 6H, H7, H9, H10, H11,
H12, H13), 6.85 (t, 1H, H6), 6.22 (d, 1H, H8), 2.50
(s, 3H, COCH3). UV–Vis in acetonitrile: kmax(nm) (emax
,
(s, 3H, COCH3). UV.–Vis. in acetonitrile: kmax(nm) (emax
,
M-1 cm-1): 358 (8.80 9 104), 294 (5.20 9 104), 210
(6.86 9 104). C21H16N4O3S, Found: C, 62.5; H, 3.7; N,
13.7%. Calculated: C, 62.4; H, 4.0; N, 13.8.
M-1 cm-1): 352 (8.83 9 104), 294 (5.24 9 104), 214
(6.90 9 104). C21H17N3OS, Found. C, 70.4; H, 5.0; N,
11.4%. Calculated: C, 70.2; H, 4.8; N, 11.7%.
Preparation of trans-[Ru(bipy)(L)Cl2]; general
procedure
1-(4-Chlorophenylhydrazono)-1-{[2-(phenylthio)
phenyl]imino}acetone (L2)
Yield = 4.1 g, 52%. M.p = 132–134 ꢁC. I.r. (KBr, cm-1):
mN=N = 1,478, mC=N = 1,599, mC=O = 1,664. H NMR (in
CDCl3): d 7.50 (d, 1H, H5), 7.30 (m, 6H, H6, H9, H10,
H11, H12, H13), 7.19 (d, 2H, H1, H3), 7.05 (1H, t, H7),
6.95 (2H, d, H2, H4), 6.22 (d, 1H, H8), 2.55 (s, 3H,
RuCl3.3H2O (0.26 g, 1.0 mmol) and (1.0 mmol) of (L)
were dissolved in absolute ethanol (100 cm3). After
refluxing for 1 h, bipy (1.0 mmol) was added and the
reaction was heated under reflux for an additional 3 h and
then an excess of LiCl (0.50 g, 11.8 mmol) was added.
After allowing the reaction mixture to reflux for an addi-
tional 1 h, the solvent was removed by rotary evaporator.
The crude product was dissolved in dichloromethane
(20 cm3) and purified by column chromatography
(50 9 3 cm) containing 250 g of grade (III) alumina. The
first pale yellow band of the azomethine ligand (L) was
eluted with hexane. Acetone was used to elute the second
dark-red band of the product.
1
COCH3). UV–Vis in acetonitrile:
kmax(nm) (emax,
M-1 cm-1): 353 (8.09 9 104), 294 (4.69 9 104), 240
(6.24 9 104). C21H16N3ClOS, Found: C, 64.1; H, 4.2; N,
10.5%. Calculated: C, 64.0; H, 4.1; N, 10.7%.
1-(4-Methoxyphenylhydrazono)-1-{[2-(phenylthio)
phenyl]imino}acetone (L3)
Yield = 4.7 g, 60%. M.p. = 105–107 ꢁC I.r. (KBr, cm-1):
mN=N = 1,491, mC=N = 1,599, mC=O = 1,675. 1H NMR
(CDCl3) d: 7.52 (d, 1H, H5), 7.25 (m, 6H, H7, H9, H10,
H11, H12, H13), 7.05 (d, 2H, H1, H3) 6.90 (t, 1H, H6),
6.85 (d, 2H, H2, H4), 6.23 (d, 1H, H8), 3.8 (s, 3H, OCH3),
2.55 (s, 3H, COCH3). UV–Vis in acetonitrile: kmax(nm)
(emax, M-1 cm-1): 351 (9.01 9 104), 297 (5.38 9 104),
245 (7.02 9 104). C22H19N3O2S, Found: C, 67.7; H, 4.8;
N, 10.5%. Calculated: C, 67.8; H, 4.9; N, 10.8%.
trans-[Ru(bipy)(L1)(Cl)2] (C1)
Yield = 0.32 g, 52%. I.r. (KBr, cm-1): mN=N = 1,485,
1
mC=N = 1,616, mC=O = 1701. H NMR (CDCl3) d 8.11 (d,
2H, H1, H3), 7.98 (d, 1H, H14), 7.9 (d, 1H, H21), 7.88
(d, 1H, H17), 7.81 (d, 1H, H18), 7.78 (d, 1H, H5), 7.70
(t, 1H, H19), 7.67 (d, 2H, H2, H4), 7.5 (d, 2H, H5, H8),
7.40 (d, 1H, H7), 7.06 (m, 7H, H6, H9, H10, H11,
H12, H13, H20), 6.90 (t,1H, H15), 6.70 (t, 1H, H16), 2.76
1-(4-bromophenylhydrazono)-1-{[2-(phenylthio)
(s, 3H, COCH3). UV–Vis in acetonitrile: kmax(nm) (emax
,
M-1 cm-1): 510 (6.870 9 103), 374 (8.710 9 103), 285
(2.979 9 104). C31H25N5OSRuCl2ꢀ0.5 H2O, Found: C,
53.5%; H, 3.8; N, 10.2%. Calculated: C, 53.2; H, 3.7; N,
10.0%.
phenyl]imino}acetone(L4)
Yield = 4.5 g, 51%. M.p. = 123–127 ꢁC. I.r. (KBr, cm-1):
mN=N = 1,478, mC=N = 1,596, mC=O 1,675. 1H NMR
123