M. Yadav et al. / Journal of Organometallic Chemistry 696 (2011) 758e763
759
Scheme 1. Synthesis of complexes of 1e4.
rhodium(III) chloride, iridium(III) chloride,
a
-phellanderene, 1,3-
2.2.2. Preparation of [(
Complex 2 was synthesized following the above procedure
using [{( -Cl)Cl}2] (0.153 g, 0.25 mmol) in place of
6-C10H14)Ru(
[{( -Cl)Cl}2]. Yield: 0.135 g, 45%. Anal. Calc. for
6-C6H6)Ru(
C29H29ClN2FeRu: C, 58.25, H, 4.89; N, 4.69%. Found: C, 58.45, H,
4.86; N, 4.83%. IR (KBr pellets, cmꢀ1): 474, 717, 766, 810, 890, 993,
1034, 1190, 1204, 1248, 1343, 1378, 1447, 1557, 2917, 3092. 1H NMR
h
6-C10H14)RuCl(fcdpm)] 2
hexadiene, pentamethylcyclopentadiene, 2,3-dicloro-5,6-dicyano-
1,4-benzoquinone (DDQ), ferrocenylcarboxaldehyde, pyrrole, silver
trifluoromethanesulfonate, triphenylphosphine and ammonium
thiocyanate (all Aldrich) were used as received without further
h
m
h
m
purifications. The precursor complexes [{(
h
6-arene)Ru(
h
5-C5Me5)M(
m-Cl)Cl}2]
-Cl)Cl}2]
(h
6-arene ¼ C6H6 [21], C10H14 [22]), [{(
m
(M ¼ Rh [23] or Ir [24]) and the ligand 5-ferrocenyldipyrromethane
were prepared and purified following the literature procedures [25].
Elemental analyses for C, H and N were performed on an Exeter
Analytical Inc. Model CE-440 Elemental Analyzer. IR and electronic
absorption spectra were acquired on a Varian 3300 FTIR and Shi-
madzu UV-1700 series spectrophotometers, respectively. 1H NMR
spectra were recorded on a JEOL AL 300 NMR spectrometer at r.t. in
CDCl3 using TMS as an internal reference.
(
d
ppm); 1.15 (d, 6H, J ¼ 6.9), 2.24 (s, 3H), 2.42 (m, 1H), 4.14 (s, 5H),
4.45 (s, 2H), 4.72 (s, 2H), 5.25 (s, 4H), 6.47 (d, 2H, J ¼ 3.3 Hz), 7.58 (d,
2H, J ¼ 3.6 Hz), 7.90 (s, 2H). UVevis. (CH2Cl2, lmax nm,
e M
ꢀ1 cmꢀ1):
506 (3.10 ꢁ 104), 434 (1.70 ꢁ 104), 340 (1.99 ꢁ 104), 248 (3.06 ꢁ 104),
230 (3.83 ꢁ 104).
2.2.3. Preparation of [(
This complex was prepared following the above procedure for 1
except that [{( -Cl)Cl}2] (0.154 g, 0.25 mmol) was
5-C5Me5)Rh(
used in place of [{( -Cl)Cl}2]. Yield: 0.117 g, 39%. Anal.
6-C6H6)Ru(
h
5-C5Me5)RhCl(fcdpm)] 3
h
m
h
m
Calc. for C29H30ClN2FeRh: C, 57.98, H, 5.03; N, 4.66%. Found: C,
57.78, H, 4.98; N, 4.54%. IR (KBr pellets, cmꢀ1): 474, 667, 720, 770,
820, 890, 990, 1030, 1185, 1204, 1248, 1338, 1393, 1460, 1533, 1557,
2.2. Syntheses
2.2.1. Preparation of [(h
6-C6H6)RuCl(fcdpm)] 1
2920, 3094. 1H NMR (
d ppm): 1.52 (s, 15H), 4.16 (s, 5H), 4.47 (s, 2H),
To an ice-cold solution of 5-ferrocenyldipyrromethane (0.165 g,
0.5 mmol) in CHCl3 (75 mL), DDQ (0.114 g, 0.5 mmol) dissolved in
benzene (50 mL) was added slowly with stirring over a period of
1 h. After TLC confirmed complete consumption of the starting
material, solvent was removed under reduced pressure and dark
red residue redissolved in CHCl3/MeOH (60 mL; 1:1 v/v) and
4.75 (s, 2H), 6.48 (d, 2H, J ¼ 3.9 Hz), 7.57 (d, 2H, J ¼ 3.9 Hz), 7.60 (s,
2H). UVevis. (CH2Cl2, lmax nm,
e
M
ꢀ1 cmꢀ1): 521 (3.08 ꢁ 104), 412
(1.89 ꢁ 104), 341 (2.41 ꢁ 104), 250 (3.50 ꢁ 104), 231 (4.81 ꢁ 104).
2.2.4. Preparation of [(
Complex 4 was prepared following the above procedure for 1
except that [{( -Cl)Cl}2] (0.199 g, 0.25 mmol) was used
5-C5Me5)Ir(
in place of [{( -Cl)Cl}2]. Yield: 0.138 g, 40%. Anal. Calc.
6-C6H6)Ru(
h
5-C5Me5)IrCl(fcdpm)] 4
filtered. Triethylamine (0.50 mL) and [{(h m-Cl)Cl}2]
6-C6H6)Ru(
h
m
(0.125 g, 0.25 mmol) were successively added to the filtrate and
heated under reflux overnight. It was allowed to cool to r.t. and
concentrated to dryness under reduced pressure to afford a black
solid which was purified by column chromatography (SiO2; CHCl3
with 10% hexane). Second bright orange band afforded the desired
h
m
for C29H30ClN2FeIr: C, 50.47, H, 4.38; N, 4.06%. Found: C, 50.52, H,
4.43; N, 4.12%. IR (KBr pellets, cmꢀ1): 473, 667, 714, 771, 820, 893,
990, 1032, 1185, 1205, 1248, 1339, 1391, 1460, 1535, 1555, 2922,
3094. 1H NMR (
d ppm): 1.51 (s,15H), 4.17 (s, 5H), 4.48 (s, 2H), 4.75 (s,
product [(h
6-C6H6)RuCl(fcdpm)] as lustrous green solid. Yield:
2H), 6.46 (d, 2H, J ¼ 3.9 Hz), 7.58 (d, 2H, J ¼ 3.9 Hz), 7.62 (s, 2H).
0.111 g, 41%. Anal. Calc. for C25H21ClN2FeRu: C, 55.42; H, 3.91; N,
5.17. Found: C, 55.74; H, 3.86; N, 5.34%. IR (KBr pellets, cmꢀ1): 480,
667, 728, 770, 810, 885, 993, 1034, 1190, 1204, 1240, 1338, 1393,
UVevis. (CH2Cl2, lmax nm,
e
Mꢀ1 cmꢀ1): 507 (2.48 ꢁ 104), 432
(2.01 ꢁ 104), 343 (2.52 ꢁ 104), 253 (3.79 ꢁ 104), 229 (5.32 ꢁ 104).
1460, 1556, 2912, 3091. 1H NMR (
d
ppm): 4.17 (s, 5H), 4.47 (s, 2H),
2.2.5. Preparation of [(
h
6-C10H14)Ru(SCN)(fcdpm)] 5
6-C10H14)RuCl(fcdpm)] (0.150 g, 0.25 mmol)
4.76 (s, 2H), 5.58 (s, 6H), 6.49 (d, 2H, J ¼ 3.3 Hz), 7.66 (d, 2H,
J ¼ 3.6 Hz), 8.01 (s, 2H). UVevis. (CH2Cl2, lmax nm,
e M
ꢀ1 cmꢀ1): 508
To a solution of [(
h
(3.21 ꢁ 104), 436 (1.25 ꢁ 104), 337 (1.62 ꢁ 104), 230 (3.83 ꢁ 104).
in dry acetone (10 mL), solid NH4SCN (0.019 g, 0.25 mmol) was
+
-
SO3CF3
Ru
(i)
N
Ru
(ii)
N
Ph3P
Ru
Cl
N
NCS
N
N
N
Fe
Fe
Fe
6
5
Scheme 2. Synthesis of complexes (i) NH4SCN/acetone, (ii)AgSO3CF3/PPh3/acetone.