as eluent to afford a pale yellow powder (82.1 mg, 57% yield),
which contained mer- and fac-isomers in 6 : 1 ratio according
to 1H NMR spectral data. Crystals of mer-3a suitable for X-
ray crystallographic determination were grown in THF solution
layered with hexane at room temperature in several days.
Synthesis of Ir(pympi)3 (3b)
Method A. The similar procedure was conducted as described
in method A of Ir(pypi)3 (3a), except 1,2-dichloroethane used in-
stead of THF. Removal of all volatiles afforded crude product con-
taining mer- and fac-isomers in 6 : 1 ratio according to 1H NMR
studies. TLC results were Rf = 0.46 for mer-Ir(pympi)3 and Rf =
0.37 for fac-Ir(pympi)3 with eluent dichloromethane–methanol =
100 : 1. The crude product was purified by flash column
chromatography on degassed silica gel using dichloromethane as
eluent to give mer-Ir(pympi)3 in 72% yield and fac-Ir(pympi)3
in 12% yield. When the reaction was performed in refluxing 2-
ethoxyethanol, mer- and fac-isomers were obtained in 3.8 : 1 ratio.
Method B.
A mixture of [Ir(l-Cl)(COD)]2 (80.4 mg,
0.120 mmol), [pypiH2][Cl] (168.4 mg, 0.730 mmol) and Ag2O
(166.4 mg, 0.718 mmol) in 2-ethoxyethanol (10 mL) was re-
fluxed at ca. 135 ◦C for 24 h under dark condition. Flash
column chromatography was performed on silica gel with elu-
ent dichloromethane afforded Ir(pypi)3 as a pale yellow solid.
(106.6 mg, 58%). The proportion of mer- and fac-isomers was
1
found to be 6 : 1 according to H NMR spectroscopy. Recrys-
Method B. A similar procedure was conducted as described
in method B of Ir(pypi)3 (3a), except that 1,2-dichloroethane was
used instead of 2-ethoxyethanol. Removal of all volatiles afforded
crude product containing mer- and fac-isomers in 4.3 : 1 ratio
tallization several times from dichloromethane solution layered
with methanol under reduced pressure afforded pure fac-complex
(15.5 mg), and mer-Ir complex (68.2 mg) was obtained as a
mixture containing 15% fac-isomer. When the reactions in the
same procedure were performed in refluxing 1,2-dichloroethane
or DMF, the yields of the product were 78 and 79%, respectively,
and the proportions of mer : fac-isomers were 16 : 1 and 3.3 : 1,
respectively).
1
according to H NMR studies. The crude product was purified
by flash column chromatography on degassed silica gel using
dichloromethane as eluent to give mer-Ir(pympi)3 in 52% yield
and fac-Ir(pympi)3 in 12% yield.
Physical data for mer-Ir(pympi)3 (mer-3b)
Physical data for mer-Ir(pypi)3 (mer-3a)
◦
◦
Mp 195 C (decomp.); 1H NMR (CDCl3, 300 MHz, 35 C) d H
1
◦
Mp 267 C (decomp.); H NMR (CDCl3, 300 MHz, 35 ◦C) d
1
◦
NMR (CDCl3, 300 MHz, 35 C) d: 3.51 (s, 3H, OCH3), 3.53 (s,
5.86–5.99 (m, 3H, Hc), 6.42–6.83 (m, 9H, Haromatic), 6.87–7.07 (m,
5H, Haromatic), 7.09–7.18 (m, 3H, Ha), 7.21–7.25 (m, 1H, Haromatic),
7.30–7.38 (m, 3H, Hf), 7.67 (s, 4H, He), 7.70 (s, 4H, He), 7.77 (s,
4H, He); 13C NMR (CDCl3, 75 MHz, 35 ◦C) d 104.36, 104.43,
104.52, 111.25, 111.55, 111.68, 111.74, 111.93, 112.07, 117.35,
117.41, 118.03, 120.00, 120.26, 120.42, 120.64, 120.96, 121.18,
125.76, 125.93, 126.18, 126.21, 126.43, 128.02, 128.13, 130.11,
130.34, 137.75, 139.98, 140.15, 145.92, 147.03, 147.94, 148.22,
149.28, 151.80, 163.42, 164.21, 166.61; MS (FAB+): m/z 772 (M+),
3H, OCH3), 3.55 (s, 3H, OCH3), 5.87 (ddd, J = 1.2, 6.3, 7.5 Hz,
1H, Hc), 5.91 (ddd, J = 1.2, 6.3, 7.5 Hz, 1H, Hc), 5.97 (ddd, J =
1.2, 6.3, 7.5 Hz, 1H, Hc), 6.03 (d, J = 2.7 Hz, 1H, Hh), 6.27 (d, J =
2.4 Hz, 1H, Hh), 6.39–6.56 (m, 8H, Haromatic), 6.62 (d, J = 3.0 Hz,
1H, Hh), 7.02–7.13 (m, 4H, Haromatic), 7.19–7.29 (m, 3H, Hf), 7.57
(s, 1H, He), 7◦.59 (s, 1H, He), 7.66 (s, 1H, He); 13C NMR (CD2Cl2,
75 MHz, 35 C) d 54.40, 54.44, 54.54, 104.01, 104.06, 104.13 (2
carbons), 104.34, 104.99, 110.91, 111.26, 111.63, 111.89, 112.10,
112.26, 116.93, 117.06, 117.54, 120.05, 120.44, 120.62, 122.53,
124.30, 124.59, 125.30, 127.26, 127.30, 129.72, 129.99, 130.05,
139.74, 140.80, 141.54, 149.80, 151.02, 153.52, 157.51, 157.55,
157.89, 161.41, 161.67, 164.32; MS (EI+): m/z 862.1 (M+); CV
(vs. Fc/Fc+ in CH2Cl2): EOX = 0.20 V, ERED = −1.46 V; IR (NaCl
film) m/cm−1: 3109, 3078, 3055, 2990, 2933, 2828, 1565, 1461, 1435,
1336, 1257, 1036, 745; UV-vis (CH2Cl2) kmax//nm (e/104 M−1 cm−1):
229 (8.00), 266 br (5.39), 310 br (2.59), 372 br (1.00). Anal. Calc.
for C42H33IrN6O3: C, 58.52; H, 3.86; N, 9.75. Found: C, 58.53; H,
3.93; N, 9.46%.
579 (M+ − pypi); CV (vs. Fc/Fc+ in CH2Cl2): EOX = 0.20 V, ERED
=
−1.44 V; IR (KBr film) m/cm−1: 3047, 2961, 1646, 1455, 1438, 1362,
1287, 1260, 1189,1148, 1081, 1042, 995, 920, 806, 744, 721; UV-vis
(CH2Cl2) kmax//nm (e/104 M−1 cm−1): 230 (7.5), 302 sh (2.8), 375
br (1.3). Anal. Calc. for C39H27IrN6 : C, 60.68; H, 3.53; N, 10.89.
Found: C, 60.73; H, 3.79; N, 10.74%.
Physical data for fac-Ir(pypi)3 (fac-3a)
Mp 241–245 ◦C (decomp.); 1H NMR (300 MHz, CDCl3, 35 ◦C) d
5.96 (ddd, J = 1.1, 6.5, 7.4 Hz, 3H, Hc), 6.51 (ddd, J = 0.7, 6.4,
9.3 Hz, 3H, Hb), 6.61 (dd, J = 0.9, 7.4 Hz, 3H, Hd), 6.70 (dd, J =
1.5, 7.3 Hz, 3H, Hgꢀ ), 6.77 (dt, J = 1.1, 7.2 Hz, 3H, Hh), 6.98 (dt,
J = 1.6, 7.4 Hz, 3H, Hg), 7.14 (td, J = 1.2, 9.4 Hz, 3H, Ha), 7.35
(dd, J = 0.8, 7.9 Hz, 3H, Hf), 7.75 (s, 3H, He); 13C NMR (CDCl3,
75 MHz, 35 ◦C) d 104.60, 111.65, 112.08, 118.07, 120.48, 120.67,
125.96, 126.44, 130.20, 137.86, 146.75, 150.09, 167.14; MS (EI+):
m/z 772.2 (M+), 579.2 (M+ − pypi); CV (vs. Fc/Fc+ in CH2Cl2):
EOX = 0.21 V, ERED = −1.42 V; IR (KBr film) m/cm−1: 3047, 2956,
2925, 2852, 1720, 1645, 1578, 1457, 1448, 1407, 1336, 1288, 1249,
1190, 1147, 1121,1075, 1042, 1018, 962, 927, 802, 743, 721; UV-vis
(CH2Cl2) kmax//nm (e/104 M−1 cm−1): 230 (5.9), 298 sh (2.8), 381
br (1.0). Anal. Calc. for C39H27IrN6·CH2Cl2: C, 56.07; H, 3.41; N,
9.81. Found: C, 56.02; H, 2.86; N, 9.49%.
Physical data for fac-Ir(pympi)3 (fac-3b)
Mp 205 ◦C (decomp.); 1H NMR (CDCl3, 300 MHz, 35 ◦C) d 3.52
(s, 9H, OCH3), 5.94 (ddd, J = 1.2, 6.5, 7.5 Hz, 3H, Hc), 6.34 (d,
J = 2.7 Hz, 3H, Hgꢀ ), 6.42–6.51 (m, 6H, Hb, g), 6.57 (ddd, J =
1.2, 2.1, 6.5 Hz, 3H, Hd), 7.08 (ddd, J = 1.2, 1.2, 9.3 Hz, 3H,
Ha), 7.24 (d, J = 8.4 Hz, 3H, Hf), 7.64 (s, 3H, He); 13C NMR
(CDCl3, 75 MHz, 35 ◦C) d 55.02, 104.33, 105.86, 111.80, 111.88,
117.72, 120.20, 122.20, 126.05, 129.85, 140.54, 152.33, 157.57,
164.89; MS (FAB+): m/z 864.2 (M+); CV (vs. Fc/Fc+ in CH2Cl2):
EOX = 0.28 V, ERED = −1.41 V; IR (NaCl film) m/cm−1: 3144,
3110, 3057, 2991, 2960, 2933, 2828, 1567, 1462, 1435, 1341, 1259,
1036, 795, 742; UV-vis (CH2Cl2) kmax//nm (e/104 M−1 cm−1): 229
(6.71), 264 br (4.65), 308 br (2.30), 396 br (0.64). Anal. Calc. for
922 | Dalton Trans., 2008, 916–923
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