842
M. Yadav et al. / Journal of Organometallic Chemistry 695 (2010) 841–849
atmosphere. The solvents were dried and distilled by standard
procedures before use [41]. Hydrated ruthenium(III) chloride,
hydrated rhodium(III) chloride, hydrated iridium(III) chloride,
2.1.4. Preparation of [(
g
6-C10H14)RuCl2(3-dpmane)] (4)
6-C10H14)Ru(
l-Cl) Cl}2]
This complex was prepared using [{(
g
(153 mg, 0.250 mmol) and 5-(3-pyridyl)dipyrromethane (112 mg,
0.500 mmol) following the above procedure for 1.Yield: 201 mg,
76%, m.p. 135 °C (decomp.). Microanalytical data: C24H27N3Cl2Ru,
requires: C, 54.44; H, 5.14; N, 7.94. Found: C, 54.75; H, 5.26; N,
7.83%. IR (KBr pellets, cmꢀ1): 3340, 3047, 1610, 1564, 1470,
1425, 1032, 1028, 971, 779, 734, 584. 1H NMR (CDCl3, d ppm):
8.92 (s, 1H), 8.86 (d, 1H, J = 5.4 Hz), 8.34 (bs, 2H), 7.53 (m, 1H),
7.20 (m, 1H), 6.71 (bs, 2H), 6.13 (d, 2H, J = 2.1 Hz), 5.85 (bs, 2H),
5.47 (s, 1H), 5.39 (d, 2H, 5.7 Hz), 5.17 (d, 2H, J = 6.0 Hz), 2.89 (m,
1H), 2.02 (s, 3H), 1.25 (d, 6H, J = 7.2 Hz). UV–Vis {CH2Cl2, k nm
pentamethylcyclopentadiene, 1,3-cyclohexadiene,
a-phellandrene
(Aldrich) were used as received. The ligands 5-(4-pyridyl)dipyr-
romethane, 5-(3-pyridyl)dipyrromethane [42] and precursor com-
plexes [{(
[44]), [{(
g
g
6-arene)Ru(
5-C5Me5)Rh(
l
l
-Cl)Cl}2] (arene = benzene [43], p-cymene
-Cl)Cl}2] [45], [{( -Cl)Cl}2]
g
5-C5Me5)Ir(
l
[46] were prepared and purified following the literature proce-
dures. Microanalyses were performed on a Exter CE-440 CHN Ana-
lyzer. IR and electronic absorption spectra were recorded on a
Perkin–Elmer-577 and Shimadzu-UV 1700 spectrophotometers,
respectively. 1H and 13C NMR spectra were acquired on a JEOL AL
300 FT-NMR machine in chloroform-d at 298 K using TMS as an
internal reference. Emission spectra were recorded in dichloro-
methane on a Varian Cary Eclipse Fluorescence spectrophotometer
at room temperature.
(e
)}: 418 (2.86 ꢁ 103), 288 (1.15 ꢁ 104), 239 (2.32 ꢁ 104).
2.1.5. Preparation of [(
g
5-C5Me5)RhCl2(4-dpmane)] (5)
5-C5Me5)Rh(
-Cl) Cl}2] (154 mg,
It was prepared from [{(
g
l
0.250 mmol) and 5-(4-pyridyl)dipyrromethane (112 mg, 0.500
mmol) following the above procedure for 1. Yield: 207 mg, 78%,
m.p. 146 °C (decomp.). Microanalytical data: C24H28N3Cl2Rh, re-
quires: C, 54.15; H, 5.30; N, 7.89. Found: C, 54.42; H, 5.42; N,
7.82%. IR (KBr pellets, cmꢀ1): 3340, 2923, 2857, 1613, 1558,
1460, 1426, 1377, 1093, 1026, 728, 673, 598, 522. 1H NMR (CDCl3,
d ppm): 8.63 (d, 2H, J = 5.1 Hz), 8.40 (bs, 2H), 7.05 (d, 2H,
J = 5.4 Hz), 6.66 (bs, 2H), 6.05 (bs, 2H), 5.71 (bs, 2H), 5.51 (s, 1H),
2.1. Syntheses
2.1.1. Preparation of [(
g
6-C6H6)RuCl2(4-dpmane)] (1)
6-C6H6)Ru(
-Cl)Cl}2] (125 mg, 0.250
To a suspension of [{(
g
l
mmol) in dichloromethane (25 mL), 5-(4-pyridyl)dipyrromethane
(112 mg, 0.500 mmol) was added and stirred at room temperature
for 4 h. It gave a clear pale red solution which was filtered through
Celite to remove any solid impurities. Addition of hexane to the fil-
trate afforded pale red crystalline product. It was separated by fil-
tration washed with diethyl ether and dried under vacuum. Yield:
1.60 (s, 15H). UV–Vis {CH2Cl2, k nm (
e
)}: 402 (3.2 ꢁ 103), 268
(9.97 ꢁ 103), 238 (2.25 ꢁ 104).
2.1.6. Preparation of [(
g
5-C5Me5)RhCl2(3-dpmane)] (6)
5-C5Me5)Rh(
l-Cl)Cl}2]
Complex was prepared from [{(
6
g
180 mg, 76%, m.p. 135 °C (decomp.). Microanalytical data: C20
-
(154 mg, 0.250 mmol) and 5-(3-pyridyl)dipyrromethane (112 mg,
0.500 mmol) following the procedure employed for 1. Yield:
202 mg, 80%, m.p. 145 °C (decomp.). Microanalytical data:
C24H28N3Cl2Rh, requires: C, 54.15; H, 5.30; N, 7.89. Found: C,
54.39; H, 5.45; N, 7.80%. IR (KBr pellets, cmꢀ1): 3352, 2925, 1613,
1567, 1468, 1426, 1117, 1032, 730, 588. 1H NMR (CDCl3, d ppm):
8.83 (d, 1H, J = 4.5 Hz), 8.80 (s, 1H), 8.25 (bs, 2H), 7.55 (m, 1H),
7.26 (m, 1H), 6.73 (bs, 2H), 6.14 (d, 2H, J = 3.0 Hz), 5.85 (bs, 2H),
H19N3Cl2Ru, requires: C, 50.75; H, 4.05; N, 8.88. Found: C, 51.04;
H, 4.20; N, 8.80%. IR (KBr pellets, cmꢀ1): 3345, 3065, 2925, 1610,
1550, 1429, 1093, 806, 673, 473. 1H NMR (CDCl3, d ppm): 8.76
(d, 2H, J = 6.0 Hz), 8.15 (bs, 2H), 7.02 (d, 2H, J = 6.0 Hz), 6.67(d,
2H, J = 0.9 Hz), 6.10 (dd, 2H, J = 3.0, 2.4 Hz), 5.77 (bs, 2H), 5.63 (s,
6H), 5.46 (s, 1H). UV–Vis {CH2Cl2, k nm (
e
)}: 413 (2.20 ꢁ 103),
290 (1.17 ꢁ 104), 242 (2.10 ꢁ 104).
5.50 (s, 1H), 1.60 (s, 15H). UV–Vis {CH2Cl2, k nm (
e)}: 401
(2.74 ꢁ 103), 268 (1.17 ꢁ 104), 239 (2.06 ꢁ 104).
2.1.2. Preparation of [(
g
6-C6H6)RuCl2(3-dpmane)] (2)
6-C6H6)Ru(
l-Cl)Cl}2] (125
Complex 2 was prepared from [{(
g
2.1.7. Preparation of [(
g
5-C5Me5)IrCl2(4-dpmane)] (7)
5-C5Me5)Ir(
l-Cl)Cl}2]
mg, 0.250 mmol) and 5-(3-pyridyl)dipyrromethane (112 mg,
0.500 mmol) following the method employed for 1. Yield:
177 mg, 75%, m.p. 139 °C (decomp.). Microanalytical data:
C20H19N3Cl2Ru, requires: C, 50.75; H, 4.05; N, 8.88. Found: C,
51.04; H, 4.18; N, 8.80%. IR (KBr pellets, cmꢀ1): 3349, 3050, 1610,
1560, 1472, 1429, 1040, 1035, 823, 734, 584. 1H NMR (CDCl3, d
ppm): 9.04 (s, 1H), 8.94 (d, 1H, J = 5.1 Hz), 8.27 (bs, 2H), 7.56 (m,
1H), 7.26 (m, 1H), 6.73 (bs, 2H), 6.15 (bs, 2H), 5.86 (bs, 2H), 5.62
This complex was prepared using [{(
g
(199 mg, 0.250 mmol) and 5-(4-pyridyl)dipyrromethane (112 mg,
0.500 mmol) following the above procedure for 1. Yield: 233 mg,
75%, m.p. 177 °C (decomp.). Microanalytical data: C24H28N3Cl2Ir,
requires: C, 46.37; H, 4.54; N, 6.76. Found: C, 46.67; H, 4.70; N,
6.67%. IR (KBr pellets, cmꢀ1): 3342, 2925, 1612, 1558, 1463,
1428, 1370, 1093, 1026, 729, 598. 1H NMR (CDCl3, d ppm):
8.75(d, 2H, J = 6.0 Hz), 8.17 (bs, 2H), 7.11(d, 2H, J = 5.7 Hz), 6.71
(bs, 2H), 6.12 (d, 2H, J = 2.1 Hz), 5.79 (bs, 2H), 5.54 (s, 1H), 1.56
(s, 6H), 5.48 (s, 1H). UV–Vis {CH2Cl2, k nm (
e
)}: 411 (2.24 ꢁ 103),
273 (1.11 ꢁ 104), 239 (1.98 ꢁ 104).
(s, 15H). UV–Vis {CH2Cl2,
k
nm
(e
)}: 445 (1.57 ꢁ 103), 280
(1.16 ꢁ 104), 238 (2.32 ꢁ 104).
2.1.3. Preparation of [(
g
6-C10H14)RuCl2(4-dpmane)] (3)
6-C10H14)Ru(
This complex was prepared using [{(
g
l-Cl) Cl}2]
2.1.8. Preparation of [(
g
5-C5Me5)IrCl2(3-dpmane)] (8)
5-C5Me5)Ir(
-Cl)Cl}2] (199 mg,
(153 mg, 0.250 mmol) and 5-(4-pyridyl)dipyrromethane (112 mg,
0.500 mmol) following the method for 1. Yield: 212 mg, 80%,
m.p. 137 °C (decomp.). Microanalytical data: C24H27N3Cl2Ru, re-
quires: C, 54.44; H, 5.14; N, 7.94. Found: C, 54.68; H, 5.29; N,
7.83%. IR (KBr pellets, cmꢀ1): 3326, 3099, 2962, 1612, 1561,
1465, 1427, 1040, 1030, 901, 774, 728, 620, 528. 1H NMR (CDCl3,
d ppm): 8.66 (d, 2H, J = 6.0 Hz), 8.28 (bs, 2H), 6.95 (d, 2H,
J = 6.0 Hz), 6.62 (bs, 2H), 6.07 (d, 2H, J = 2.1 Hz), 5.77 (bs, 2H),
5.43 (d, 3H, J = 5.7 Hz), 5.21 (d, 2H, 5.7 Hz), 2.98 (m, 1H), 2.06 (s,
It was prepared from [{(
g
l
0.250 mmol) and 5-(3-pyridyl)dipyrromethane (112 mg, 0.500
mmol) following the above procedure for 1. Yield: 230 mg, 74%,
m.p. 175 °C (decomp.). Microanalytical data: C24H28N3Cl2Ir, re-
quires: C, 46.37; H, 4.54; N, 6.76. Found: C, 46.69; H, 4.68; N,
6.70%. IR (KBr pellets, cmꢀ1): 3350, 2923, 1615, 1570, 1464,
1427, 1110, 1030, 729, 585. 1H NMR (CDCl3, d ppm): 8.86 (d, 1H,
J = 4.8 Hz), 8.80 (s, 1H), 8.28 (bs, 2H), 7.57 (m, 1H), 7.26 (m, 1H),
6.74 (bs, 2H), 6.14 (d, 2H, J = 3.0 Hz), 5.86 (bs, 2H), 5.52 (s, 1H),
3H), 1.30 (d, 6H, J = 6.9). UV–Vis {CH2Cl2,
k
nm
(
e)}: 416
1.56 (s, 15H). UV–Vis {CH2Cl2, k nm (
e
)}: 435 (9.27 ꢁ 102), 276
(2.2 ꢁ 103), 294 (1.15 ꢁ 104), 239 (2.30 ꢁ 104).
(1.16 ꢁ 104), 240 (2.06 ꢁ 104).