RSC Advances
Paper
+
1
1
7
4
30.1, 130.5, 137.3, 137.4, 137.9, 139.7 (ArC), 140.6 (NCHN ), NCH
2
-Mes), 5.87–5.94 (1H, m, OCH ring), 6.21 (1H, s, ArH-BI),
75.8 (OCCH(CH ) ). Anal. calc. for C H BrN O : C, 66.03; H, 6.41 (1H, d, J ¼ 14.8 Hz, NCH -Mes), 6.86 (2H, s, ArH-Mes), 7.23
3
2
29 39
2
2
2
+
13
ꢀ
.45; N, 5.31. Found: C, 65.97; H, 7.44; N, 5.29. LC-MS (ESI ): m/z (1H, s, ArH-BI). C NMR (100.6 MHz, CDCl , TMS, 25 C, ppm):
3
+
47.3 [M ꢁ Br] .
d ¼ 20.4, 20.5, 21.1, 21.2 (CH -Mes + Ar-CH -BI), 25.3, 26.3, 28.7,
3
3
ꢀ
2
d. White solid, Mp: 199–200 C. Yield: 1.02 g, 94%. IR: n 30.6, 32.0, 32.8, 35.0, 36.8 (8 ꢂ CH
2 2
), 49.1 (NCH -Mes), 51.8,
ꢁ1
1
ꢀ
(
lm) 1727 cm (C]O). H NMR (400 MHz, CDCl
ppm): d ¼ 0.74 (9H, s, C(CH ), 1.59–1.73, 1.85–1.89, 1.99–2.05, (2 ꢂ COD-CH), 112.2, 112.5, 128.3, 129.8, 131.2, 131.3, 132.2,
.14–2.42, (8H, 4m, 4 ꢂ CH ), 2.05, 2.14, 2.31, 2.42 (15H, 4s, 134.7, 138.2, 138.6 (ArC), 190.3 (Ir-Ccarbene). Anal. calc. for
CH -Mes + Ar-CH -BI), 4.80–4.89 (1H, m, NCH ring), 5.15–5.21
3
, TMS, 25 C, 53.0 (2 ꢂ COD-CH), 68.0 (CHN ring), 70.5 (CHO ring), 85.6, 86.6
3 3
)
2
2
3
3
C
33
H
2
44ClIrN O: C, 55.64; H, 6.23; N, 3.93. Found: C, 55.57; H,
+
191
193
(
(
(
1H, m, OCH ring), 5.86 (2H, dd, J ¼ 14.8 Hz, NCH -Mes), 6.92 6.18; N, 3.90. LC-MS (ESI ): m/z 675.0 ( Ir), 677.0 ( Ir)
2
+
2H, s, ArH-Mes), 7.05 (1H, s, ArH-BI), 7.71 (1H, s, ArH-BI), 10.59 [M ꢁ Cl] .
+
13
ꢀ
ꢁ1
1
1H, s, NCHN ). C NMR (100.6 MHz, CDCl , TMS, 25 C, ppm):
3b. Yield: 121 mg, 80%. IR: n (lm) 1739 cm (C]O). H
3
ꢀ
d ¼ 19.7, 20.0 (CH
), 26.1 (C(CH
-Mes), 60.4 (CHN ring), 74.5 (CHO ring), 112.8, 113.2, 2.22, 2.26, 2.31 (15H, 4s, CH
24.7, 129.0, 129.4, 129.8, 136.6, 136.8, 137.5, 139.0 (ArC), 139.8 m, COD-CH), 3.71–3.74 (1H, m, COD-CH), 4.64–4.71 (2H, m,
3
-Mes), 20.2, 20.5 (2 ꢂ Ar-CH
3
-BI), 22.9, 24.0 (2 NMR (400 MHz, CDCl
3
, TMS, 25 C, ppm): d ¼ 1.52–1.74, 1.85–
ꢂ CH
2
3
)
3
), 30.7, 30.8 (2 ꢂ CH ), 37.8 (C(CH
2
3
)
3
), 46.7 1.99, 2.35–2.42 (16H, 3m, 8 ꢂ CH
2
), 1.81 (3H, s, OCCH
3
), 2.04,
(NCH
2
3
-Mes + Ar-CH
3
-BI), 3.11–3.15 (1H,
1
+
(NCHN ), 176.4 (OCC(CH
3
)
3
). Anal. calc. for C30
H
41BrN
2
O
2
: C, COD-CH), 5.69–5.75 (1H, m, NCH ring), 5.90 (2H, dd, J ¼ 14.8
6
6.53; H, 7.63; N, 5.17. Found: C, 66.50; H, 7.66; N, 5.14. LC-MS Hz, NCH -Mes), 5.99–6.02 (1H, m, OCH ring), 6.18 (1H, s, ArH-
2
+
+
13
(ESI ): m/z 461.3 [M ꢁ Br] .
BI), 6.88 (2H, s, ArH-Mes), 7.25 (1H, s, ArH-BI). C NMR (100.6
ꢀ
ꢀ
2
e. White solid, Mp: 226–227 C. Yield: 1.06 g, 95%. IR: n MHz, CDCl , TMS, 25 C, ppm): d ¼ 20.3, 20.6, 20.7, 21.0 (CH -
3
3
ꢁ1
1
ꢀ
(lm) 1716 cm (C]O). H NMR (400 MHz, CDCl
3
, TMS, 25 C, Mes + Ar-CH
3
-BI), 21.1 (OCCH
), 49.0 (NCH
64.4 (CHN ring), 71.9 (CHO ring), 84.9, 85.0 (2 ꢂ COD-CH),
-BI), 5.02–5.08 (1H, 111.8, 112.1, 128.5, 129.6, 130.9, 131.0, 131.6, 134.6, 137.9 (ArC),
), 191.3 (Ir-Ccarbene). Anal. calc. for
4.8 Hz, NCH -Mes), 6.81 (2H, s, ArH-Mes), 6.88 (1H, s, ArH-BI), C H ClIrN O : C, 55.72; H, 6.15; N, 3.71. Found: C, 55.78;
3
), 24.4, 25.1, 28.9, 29.8, 30.2, 32.5,
ppm): d ¼ 1.67–1.69, 1.74–1.80, 1.95–1.98, 2.04–2.07, 2.53–2.56, 32.9, 34.1 (8 ꢂ CH
8H, 5m, 4 ꢂ CH ), 2.13, (6H, s, CH -Mes), 2.20 (3H, s, Ar-CH
BI), 2.27 (6H, s, CH -Mes), 2.29 (3H, s, Ar-CH
2
2
-Mes), 51.8, 53.2 (2 ꢂ COD-CH),
(
2
3
3
-
3
3
m, NCH ring), 5.50–5.56 (1H, m, OCH ring), 5.73 (2H, dd, J ¼ 169.8 (OCCH
3
1
7
2
35 46
2 2
+
191
193
.32 (2H, t, J ¼ 8.4 Hz, ArH), 7.48–7.52 (1H, m, ArH), 7.58 (1H, s, H, 6.17; N, 3.73. LC-MS (ESI ): m/z 717.2 ( Ir), 719.2 ( Ir)
+
13
+
ArH-BI), 7.72 (2H, d, J ¼ 7.2 Hz, ArH), 10.77 (1H, s, NCHN ).
C
[M ꢁ Cl] .
ꢀ
ꢁ1
1
NMR (100.6 MHz, CDCl
3
, TMS, 25 C, ppm): d ¼ 20.2, 20.8 (CH
3
-
3c. Yield: 118 mg, 76%. IR: n (lm) 1734 cm (C]O). H
ꢀ
Mes), 20.7, 21.2, (2 ꢂ Ar-CH
CH ), 47.2 (NCH -Mes), 62.2 (CHN ring), 74.5 (CHO ring), 113.4, 7.2 Hz, CH(CH
14.2, 125.4, 128.4, 129.1, 129.7, 129.9, 130.1, 130.2, 133.4, 1.74–1.86, 1.88–1.95, 2.08–2.17, 2.20–2.45 (17H, 5m, 8 ꢂ CH
3
-BI), 23.9, 24.7, 30.8, 31.6 (4 ꢂ NMR (400 MHz, CDCl
3
, TMS, 25 C, ppm): d ¼ 0.70 (3H, d, J ¼
2
2
3
)
2
), 0.91 (3H, d, J ¼ 7.2 Hz, CH(CH
3 2
) ), 1.52–1.64,
1
1
2
+
+
3 2 3 3
37.2, 137.3, 138.2, 139.6 (ArC), 141.3 (NCHN ), 165.3 CH(CH ) ), 2.02, 2.23, 2.24, 2.32 (15H, 4s, CH -Mes + Ar-CH -BI),
(
4
OC(C H )). Anal. calc. for C H BrN O : C, 68.44; H, 6.64; N, 3.13–3.17 (1H, m, COD-CH), 3.75–3.80 (1H, m, COD-CH), 4.66–
6 5 32 37 2 2
.99. Found: C, 68.39; H, 6.62; N, 5.02. LC-MS (ESI ): m/z 481.2 4.71 (2H, m, COD-CH), 5.65–5.71 (1H, m, NCH ring), 5.86 (2H,
+
+
[M ꢁ Br] .
dd, J ¼ 14.8 Hz, NCH -Mes), 6.00–6.07 (1H, m, OCH ring), 6.09
2
1
3
(
1H, s, ArH-BI), 6.89 (2H, s, ArH-Mes), 7.22 (1H, s, ArH-BI).
C
ꢀ
NMR (100.6 MHz, CDCl
3
, TMS, 25 C, ppm): d ¼ 18.4, 18.6
General procedure for the synthesis of iridium(I)–NHC
complexes (3a–e)
(
CH(CH
5.3, 29.0, 29.6 (4 ꢂ CH
), 49.0 (NCH
O (23 mg, 0.1 mmol) was suspended in degassed dichloro- (CHN ring), 71.6 (CHO ring), 84.8, 84.9 (2 ꢂ COD-CH), 111.6,
methane (5 mL) and stirred at ambient temperature for 1 h 111.8, 128.5, 129.5, 130.8, 13.9, 131.5, 134.6, 138.0 (ArC), 176.0
shielded from light. [IrCl(COD)]
(67 mg, 0.1 mmol) was then (OCH(CH ), 191.3 (Ir-Ccarbene). Anal. calc. for C37 50ClIrN
added to the suspension and the reaction mixture was stirred at C, 56.79; H, 6.44; N, 3.58. Found: C, 56.84; H, 6.47; N, 3.61. LC-
3
)
2
), 20.2, 20.3, 20.6, 20.9 (CH
), 30.3 (CH(CH
-Mes), 51.6, 53.0 (2 ꢂ COD-CH), 64.5
3
-Mes + Ar-CH
3
-BI), 24.4,
2
2
3 2
) ), 32.5, 33.1, 33.9, 34.0
Under an argon atmosphere, a mixture of 2a–e (0.2 mmol) and (4 ꢂ CH
2
2
Ag
2
)
H
O :
2 2
2
3
2
+
191
193
+
ambient temperature for more 12 h. The resulting suspension MS (ESI ): m/z 745.1 ( Ir), 747.1 ( Ir) [M ꢁ Cl] .
ꢁ
1
1
was ltered over Celite®. The remaining solid was washed with
3d. Yield: 124 mg, 78%. IR: n (lm) 1728 cm (C]O). H
ꢀ
dichloromethane (2 ꢂ 5 mL) and the solvent of the ltrate was NMR (400 MHz, CDCl
3
, TMS, 25 C, ppm): d ¼ 0.74 (9H, s,
3 3
evaporated. The residue was puried by column chromatog- C(CH ) ), 1.44–1.58, 1.66–1.73, 1.82–1.90, 1.99–2.09, 2.13–2.27,
raphy on silica gel (eluent: dichloromethane) to give pure 2.38–2.41, (16H, 6m, 8 ꢂ CH
), 1.94, 2.16, 2.17, 2.25 (15H, 4s,
CH -Mes + Ar-CH -BI), 3.05–3.10 (1H, m, COD-CH), 3.68–3.71
2
complex as a yellow solid.
3
3
ꢁ
1
1
3
a. Yield: 119 mg, 84%. IR: n (lm) 3418 cm (OH). H NMR (1H, m, COD-CH), 4.57–4.63 (2H, m, COD-CH), 5.57–5.64 (1H,
ꢀ
(
2
400 MHz, CDCl
3
, TMS, 25 C, ppm): d ¼ 1.47–1.79, 1.88–2.01, m, NCH ring), 5.73 (2H, dd, J ¼ 14.8 Hz, NCH
2
-Mes), 5.99 (1H, s,
.17–2.37 (16H, 3m, 8 ꢂ CH ), 2.04, 2.25, 2.26, 2.29 (15H, 4s, ArH-BI), 6.01–6.05 (1H, m, OCH ring), 6.83 (2H, s, ArH-Mes),
2
13
ꢀ
CH -Mes + Ar-CH -BI), 3.01–3.08 (2H, m, COD-CH), 3.56 (1H, d, J 7.19 (1H, s, ArH-BI). C NMR (100.6 MHz, CDCl
3
, TMS, 25 C,
-BI), 24.6, 25.7
3 3
) ), 29.4, 29.5, 30.8, 32.9, 33.5, 33.8
3
3
¼
10.4 Hz, OH), 4.11–4.14 (1H, m, NCH ring), 4.65–4.70 (1H, m, ppm): d ¼ 20.3, 20.4, 20.8, 21.1 (CH
3 3
-Mes + Ar-CH
COD-CH), 4.75–4.80 (1H, m, COD-CH), 5.55 (1H, d, J ¼ 14.8 Hz, (2 ꢂ CH ), 26.7 (C(CH
2
26228 | RSC Adv., 2014, 4, 26222–26230
This journal is © The Royal Society of Chemistry 2014