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H-3); 7.80 (1H, dd, J = 2.20, 9.10 Hz, H-6); 7.44 (1H, ddd, J = NaOAc (0.0358 g, 0.436 mmol) was made in anhydrous CH3CN
1.19, 4.82, 7.57 Hz, H-16). 13C{1H} NMR (101 MHz, DMSO-d6): (20.0 mL) and refluxed under nitrogen for 48 h. Yield:
δ (ppm) = 152.28 (C-2), 149.73 (C-17), 149.34 (C-13), 149.12 0.0481 g, (32.3%).1H NMR (400 MHz, CDCl3): δ (ppm) = 9.05
(C-10), 147.86 (C-12), 140.33 (C-8), 137.34 (C-15), 135.33 (C-4), (1H, d, J = 4.64 Hz, H-2); 8.27 (1H, d, J = 1.74 Hz, H-8); 8.18
128.94 (C-7), 128.03 (C-9), 125.48 (C-6), 125.34 (C-11), 123.47 (1H, d, J = 9.12 Hz, H-5); 8.10 (1H, s, H-11); 7.65 (1H, dd, J =
(C-16), 120.36 (C-5), 119.95 (C-14), 117.19 (C-3). IR (ATR): (νmax
cm−1) 1606 (CvN)pyridyl, 1567 (CvN)quinoline. Melting point: H-3); 7.34 (1H, d, J = 7.58 Hz, H-14); 6.69 (1H, d, J = 7.45 Hz,
153.8–155.1 °C. Purity: 98.7% by LC (tR 2.51 min).
H-15); 2.30 (3H, s, H-17); 1.81 (15H, s, H-21). 13C{1H} NMR
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2.05, 9.11 Hz, H-6); 7.60 (1H, s, H-18); 7.50 (1H, d, J = 4.65 Hz,
7-Chloro-4-(4-(ferrocenyl)-1H-1,2,3-triazol-1-yl)quinoline (2g). (101 MHz, CDCl3): 159.68 (C-12), 158.64 (C-19), 151.67 (C-2),
To a solution of 1 (0.100 g, 0.489 mmol) and ethynylferrocene 150.46 (C-9), 140.65 (C-16), 139.29 (C-7), 137.11 (C-4), 136.98
(0.103 g, 0.489 mmol) in dichloromethane (2.00 mL), a solu- (C-18), 132.01 (C-13), 129.70 (C-6), 129.27 (C-8), 124.88 (C-5),
tion of sodium ascorbate and CuSO2·5H2O in water (2.00 mL) 123.74 (C-15), 121.98 (C-14), 120.27 (C-10), 118.12 (C-11),
was added and the reaction mixture was left to stir for 20 h at 115.92 (C-3), 88.89 (C-20), 21.92 (C-17), 9.25 (C-21); IR (ATR):
30 °C. Yield: 0.142 g (70.2%). 1H NMR (400 MHz, CDCl3): (νmax/cm−1) 1609, 1591, 1560 (Ar CvN). Melting point: 290 °C
δ (ppm) = 9.07 (1H, d, J = 2.04 Hz, H-2); 8.25 (1H, d, J = 1.51 dec. MS (HR-ESI, m/z): 647.1555 (100%, [M − Cl]+), calculated
Hz, H-8); 8.09 (1H, d, J = 9.00 Hz, H-5); 7.89 (1H, s, H-11); 7.62 647.1554.
(1H, dd, J = 1.40, 8.92 Hz, H-6); 7.53 (1H, d, J = 2.81 Hz, H-3);
Ir(III) triazole-propylphenyl complex (3c). A solution of
4.83 (2H, br s, H-14); 4.40 (2H, br s, H-15); 4.16 (5H, s, H-16). 2c (0.0510 g, 0.146 mmol), [IrCp*(μ-Cl)Cl]2 (0.0815 g,
13C{1H} NMR (101 MHz, CDCl3): δ (ppm) = 151.57 (C-2), 0.102 mmol) and NaOAc (0.0359 g, 0.438 mmol) was made in
150.51 (C-9), 148.26 (C-12), 141.12 (C-7), 137.06 (d, C-4, C-13), anhydrous CH3CN (10.0 mL) and refluxed under argon for
129.57 (C-6), 128.96 (C-8), 124.79 (C-5), 120.60 (C-10), 120.16 72 h. Yield: 0.0618 g (85.2%). 1H NMR (400 MHz, CDCl3): δ
(C-11), 115.70 (C-3), 71.45–70.98 (m, C-16), 70.61–70.20 (m, (ppm) = 9.05 (1H, d, J = 4.64 Hz, H-2); 8.27 (1H, d, J = 1.74 Hz,
C-15), 68.26–67.92 (m, C-14). IR (ATR): (νmax/cm−1) 1611, 1591, H-8); 8.18 (1H, d, J = 9.12 Hz, H-5); 8.10 (1H, s, H-11); 7.65 (1H,
1558 (Ar CvN). Melting point: 203.0–204.6 °C. MS (HR-ESI, dd, J = 2.05, 9.11 Hz, H-6); 7.60 (1H, s, H-20); 7.50 (1H, d, J =
m/z): 414.0333 (60%, [M]+), calculated 414.0335.
4.65 Hz, H-3); 7.34 (1H, d, J = 7.58 Hz, H-14); 6.69 (1H, d, J =
General procedure for the synthesis of cyclometallated Ir(III) 7.45 Hz, H-15); 2.68–2.49 (2H, m, H-17); 1.81 (15H, s, H-23);
half-sandwich complexes (3a–3e). A solution of the desired 1.75–1.63 (2H, m, H-18); 0.98 (3H, t, J = 7.26, 7.26 Hz, H-19).
ligand (1 eq.), [IrCp*(μ-Cl)Cl]2 (0.7 eq.) and NaOAc (2 eq.) was 13C{1H} NMR (101 MHz, CDCl3): 159.59 (C-12), 158.69 (C-21),
made in anhydrous CH3CN (20.0 mL). The reaction mixture 151.66 (C-2), 150.42 (C-9), 143.98 (C-16), 140.68 (C-7), 137.12
was refluxed under argon at 65–75 °C for 48–72 h and then left (C-4), 136.45 (C-20), 132.24 (C-13), 129.71 (C-6), 129.24 (C-8),
to stir at room temperature for a further 72 h, after which a 124.88 (C-5), 123.17 (C-15), 122.00 (C-14), 120.31 (C-10), 118.16
yellow precipitate formed. This precipitate was filtered and (C-11), 115.96 (C-3), 88.90 (C-22), 38.56 (C-17), 24.81 (C-18),
washed with CH3CN. The resulting yellow powder was dis- 14.17 (C-19), 9.23 (C-23). IR (ATR): (νmax/cm−1) 2869, 2925,
solved in dichloromethane and filtered through Celite™ to 2954, 1607, 1594, 1561 (Ar CvN). Melting point: 283 °C dec.
remove any excess NaOAc. The solvent was then reduced and MS (HR-ESI, m/z): 753.1960 (100%, [M − Cl + DMSO]+), calcu-
Et2O was added to produce a yellow precipitate, which was lated 753.2005.
then filtered and dried.
Ir(III) triazole-4-(trifluoromethyl)phenyl complex (3d). A solu-
Ir(III) triazole-phenyl complex (3a). A solution of 2a (0.100 g, tion of 2d (0.050 g, 0.133 mmol), [IrCp*(μ-Cl)Cl]2 (0.0744 g,
0.326 mmol), [IrCp*(μ-Cl)Cl]2 (0.182 g, 0.229 mmol) and 0.0934 mmol) and NaOAc (0.0328 g, 0.400 mmol) was made in
NaOAc (0.0535 g, 0.652 mmol) was made in anhydrous CH3CN anhydrous CH3CN (10.0 mL) and refluxed at 75 °C under
(20.0 mL) and refluxed under nitrogen for 72 h. Yield: 0.128 g argon for 72 h. Yield: 0.0121 g (12.3%). 1H NMR (400 MHz,
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(58.9%). H NMR (400 MHz, CDCl3): δ (ppm) = 9.06 (1H, d, J = CDCl3): δ (ppm) = 9.09 (1H, d, J = 4.65 Hz, H-2), 8.29 (1H, d, J =
4.62 Hz, H-2); 8.27 (1H, d, J = 1.80 Hz, H-8); 8.14–8.16 (2H, m, 2.02 Hz, H-8), 8.22 (1H, s, H-11), 8.05 (1H, d, J = 9.30 Hz, H-5),
H-5, 11); 7.79 (1H, d, J = 7.55, H-14); 7.65 (1H, dd, J = 1.97, 9.11 8.04 (1H, s, H-18), 7.66 (1H, dd, J = 2.09, 9.11 Hz, H-6),
Hz, H-6); 7.50 (1H, d, J = 4.63 Hz, H-3); 7.44 (1H, d, J = 7.42 Hz, 7.51–7.58 (2H, m, H-3, 14), 7.20 (1H, dd, J = 0.90, 7.91 Hz,
H-17); 7.06 (1H, t, J = 7.24 Hz, H-15); 6.88 (1H, t, J = 7.33 Hz, H-15), 1.81 (15H, s, H-21); 13C{1H} NMR (101 MHz, CDCl3):
H-16); 1.81 (15H, s, H-20). 13C{1H} NMR (101 MHz, CDCl3): 160.21 (C-12), 157.68 (C-19), 151.57 (C-2), 150.57 (C-9), 140.61
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159.74 (C-12), 158.61 (C-18), 151.70 (C-2), 150.44 (C-9), 140.59 (C-13), 138.27 (C-7), 137.48 (C-4), 132.60 (br q, JC–F = 3.45 Hz,
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(C-7), 137.13 (C-4), 136.23 (C-14), 134.75 (C-13), 129.74 (br s, C-18), 130.62 (q, JC–F = 30.75 Hz, C-16), 130.10 (C-6), 129.49
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2C, C-6, 15), 129.29 (C-8), 124.77 (C-5), 122.72 (C-16), 122.27 (C-8), 124.68 (q, JC–F = 273.14 Hz, C-17), 124.33 (C-5), 122.00
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(C-17), 120.28 (C-10), 118.66 (C-11), 116.02 (C-3), 89.00 (C-19), (C-11), 120.41 (C-10), 119.79 (br q, JC–F = 3.58 Hz, C-15),
9.25 (C-20). IR (ATR): (νmax/cm−1) 1611, 1586, 1560 (Ar CvN). 119.63 (C-14), 116.21 (C-3), 89.45 (C-20), 9.20 (C-21). 19F{1H}
Melting point: >280 °C dec. MS (HR-ESI, m/z): 633.1409 (100%, NMR (377 MHz, CDCl3): δ (ppm) = −62.13 (s). IR (ATR): (νmax
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[M − Cl]+), calculated 633.1397. cm−1) 1618, 1606, 1595, 1560 (Ar CvN), 1314 (C–F stretch).
Ir(III) triazole-p-tolyl complex (3b). A solution of 2b (0.0700 g, Melting point: 280 °C dec. MS (HR-ESI, m/z): 779.1396 (100%,
0.218 mmol), [IrCp*(μ-Cl)Cl]2 (0.122 g, 0.153 mmol) and [M − Cl + DMSO]+), calculated 779.1410.
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Dalton Trans.