Please do not adjust margins
Dalton Transactions
Page 8 of 12
ARTICLE
Journal Name
(Ph), 133.94 (Ph), 132.45 (Ph), 131.25 (Ph), 130.87 (Ph), 130.16 (C(CH3)3), 31.68 (C(CH3)3), 8.55 (C, Cp*); 31P NMR (162 MHz,
(Ph), 127.96 (Ph), 127.61 (Ph), 124.63 (d, J = 12.3 Hz, Ph), DMSO) δ -3.00 (s), -144.19 (hept); 19F NMR (376 MHz, DMSO) δ
DOI: 10.1039/C9DT00218A
-
116.51 (Ph), 113.63 (Ph), 113.02 (Ph), 110.12 (Ph), 48.13 (CH2), -70.16 (d); HRMS (ESI) calcd for C39H41ClIrNOP [M - PF6 ]
35.06 (C(CH3)3), 31.84 (C(CH3)3), 31.79 (CH2), 19.88 (CH2), 14.11 798.2244, found 798.2210.
(CH3); HRMS (ESI) calcd for C28H30N3O [M – I-] 424.2389, found 2: 75 % Isolated yield (yellow solid): FT-IR (KBr) : 2970 (w),
424.2373.
1593 (m), 1529 (w), 1457 (m), 1425 (w), 1314 (w), 1258 (m),
1
6c: Using 6b (1 mmol), iodomethane (CH3I) (2 mmol), 92 % 1155 (w), 1075 (w), 1035 (w), 836 (s), 764 (w), 549 (m); H
Isolated yield (pale yellow solid): 1H NMR (400 MHz, DMSO) δ NMR (400 MHz, DMSO) δ 7.80 (t, J = 8.9 Hz, 2H, Ph), 7.59 (d, J
10.15 (s, 1H, CH, benzoimidazole), 8.57 - 8.49 (m, 1H, Ph), 8.22 = 9.3 Hz, 1H, Ph), 7.35 (d, J = 10.2 Hz, 2H, Ph), 6.85 (d, J = 8.0
(d, J = 8.4 Hz, 1H, Ph), 8.00 (s, 3H, Ph), 7.76 (t, J = 7.8 Hz, 1H, Hz, 1H, Ph), 6.72- 6.59 (m, 2H, Ph), 1.54 (s, 15H, H, Cp*), 1.40
Ph), 7.62 (t, J = 7.8 Hz, 1H, Ph), 7.56 (d, J = 9.1 Hz, 1H, Ph), 7.49 (s, 9H, Ph-C(CH3)3 ); 13C NMR (101 MHz, DMSO) δ 168.40 (C,
(d, J = 8.3 Hz, 1H, Ph), 7.46 (dt, J = 4.1, 2.0 Hz, 2H, Ph), 4.30 (s, benzoxazole), 159.26 (Ph), 149.37 (Ph), 147.88 (Ph), 138.67
3H, CH3), 1.26 (s, 9H, Ph-C(CH3)3);13C NMR (101 MHz, DMSO) δ (Ph), 134.72 (Ph), 128.25 (Ph), 124.46 (Ph), 123.56 (Ph), 116.54
158.80 (C, benzoxazole), 148.74 (C, benzoimidazole), 148.00 (Ph), 114.92 (Ph), 112.14 (Ph), 111.19 (Ph), 35.65 (C(CH3)3),
(Ph), 145.10 (Ph), 141.16 (Ph), 133.72 (Ph), 132.67 (Ph), 132.02 31.96 (C(CH3)3), 9.14 (C, Cp*); 31P NMR (162 MHz, DMSO) δ -
(Ph), 131.14 (Ph), 130.86 (Ph), 130.29 (Ph), 128.03 (Ph), 127.25 144.20 (hept);19F NMR (376 MHz, DMSO) δ -70.55 (d); HRMS
-
(Ph), 124.65 (Ph), 124.10 (Ph), 116.83 (Ph), 114.44 (Ph), 113.36 (ESI) calcd for C27H31IrNO2 [M –PF6 ]594.1984, found594.1970.
(Ph), 110.61 (Ph), 35.15 (CH3), 34.22 (C(CH3)3), 31.88 (C(CH3)3); General procedure for the synthesis of complexes 3-7 was
HRMS (ESI) calcd for C25H24N3O [M – I-] 382.1919, found according the previous report. 43
382.1935.
3: 63 % Isolated yield (yellow solid): FT-IR (KBr) : 2954 (s),
7c: 7b (1 mmol), iodomethane (CH3I) (2 mmol), 96 % Isolated 1616 (m), 1489 (s), 1473 (w), 1417 (w), 1346 (m), 1266 (w),
yield (yellow solid): 1H NMR (400 MHz, DMSO) δ 10.18 (s, 1H, 1091 (w), 1067 (w), 1019 (m), 844 (s), 773 (m), 549 (s); 1H NMR
CH, benzoimidazole ), 8.58 (d, J = 2.6 Hz, 1H, Ph), 8.23 (d, J = (400 MHz, DMSO) δ 8.30 (d, J = 1.6 Hz, 1H, CH, imidazole), 8.20
8.3 Hz, 1H, Ph), 8.04 (s, 3H, Ph), 7.77 (t, J = 7.7 Hz, 1H, Ph), 7.69 (d, J = 7.8 Hz, 1H, Ph), 7.99- 7.95 (m, 1H, Ph), 7.93 (dd, J = 6.6,
(d, J = 8.0 Hz, 1H, Ph), 7.62 (t, J = 7.7 Hz, 1H, Ph), 7.52 (dd, J = 2.0 Hz, 2H, Ph), 7.88 (d, J = 8.8 Hz, 1H, Ph), 7.81 (t, J = 7.6 Hz,
13.9, 8.1 Hz, 2H, Ph), 7.42 (t, J = 7.5 Hz, 1H, Ph), 7.34 (t, J = 7.5 1H, Ph), 7.74 (d, J = 8.0 Hz, 1H, Ph), 7.68 (dd, J = 8.8, 1.8 Hz, 1H,
Hz, 1H, Ph), 4.30 (s, 3H, CH3);13C NMR (101 MHz, DMSO) δ CH, imidazole), 4.41 (td, J = 12.2, 4.9 Hz, 1H, CH2), 4.13 -3.95
158.72 (C, benzoxazole), 149.93 (C, benzoimidazole), 145.10 (m, 1H, CH2), 1.44 -1.39 (m, 4H, CH2), 1.35 (s, 9H, Ph-C(CH3)3 ),
(Ph), 141.11 (Ph), 133.88 ( Ph), 132.70 (Ph), 132.01 (Ph), 1.32 (s, 15H, H, Cp*), 0.95 (t, J = 7.4 Hz, 3H, CH3); 13C NMR (101
131.23 (Ph), 131.11 (Ph), 130.29 (Ph), 128.01 (Ph), 127.26 (Ph), MHz, DMSO) δ 163.07 (C, benzoxazole), 157.41 (C, imidazole),
126.95 (Ph), 125.66 (Ph), 124.02 (Ph), 120.67 (Ph), 114.36 (Ph), 148.80 (Ph), 148.42 (Ph), 139.01 (Ph), 137.75 (C, imidazole),
113.37 (Ph), 111.44 (Ph), 34.19 (CH3); HRMS (ESI) calcd for 134.84 (Ph), 134.66 (Ph), 133.76 (Ph), 129.31 (C, imidazole),
C21H16N3O [M – I-] 326.1293, found 326.1268.
126.02 (Ph), 125.72 (d, J = 27.3 Hz, Ph), 124.59 (Ph), 120.35
(Ph), 118.86 (Ph), 111.62 (Ph), 50.83 (CH2), 35.30 (C(CH3)3),
32.89 (CH2), 31.64 (C(CH3)3), 19.89 (CH2), 14.04 (CH3), 8.58 (C,
Cp*); 31P NMR (162 MHz, DMSO) δ-144.21 (hept); 19F NMR
(377 MHz, DMSO) δ -70.11 (d); HRMS (ESI) calcd for
Synthesis of 1-7
General procedure for the synthesis of complexes 1-2 was
according the previous report. 48
-
C35H42ClF6IrN3OP [M - PF6 ] 736.2646, found 736.2643.
Ligands 1a (or 2a) (0.1 mmol) with [Cp*IrCl2]2 (40 mg, 0.05
mmol) were added to a 25 mL Schlenk flask. Added into 2 mL
warmed to 82 °C for 14 h. Then ammonium
hexafluorophosphate (NH4PF6) (48.9 mg, 0.3 mmol) was
added. By centrifugal separation, the corresponding products
1 (or 2) was obtained.
1: 89 % Isolated yield (yellow solid): FT-IR (KBr) : 2975 (w),
1635 (m), 1485 (w), 1434 (m), 1353 (m), 1278 (w), 1111 (w),
836 (s), 778 (w), 738 (w), 692 (w), 565 (m), 536 (w); H NMR
(400 MHz, DMSO) δ 8.50 (dd, J = 7.4, 3.6 Hz, 1H, Ph), 8.10 (dt, J
= 14.8, 7.7 Hz, 2H, Ph), 7.99 (t, J = 7.6 Hz, 1H, Ph), 7.95- 7.82
(m, 4H, Ph), 7.80 - 7.69 (m, 4H, Ph), 7.24- 7.03 (m, 5H, Ph), 1.35
(s, 25H, Cp*, Ph-C(CH3)3 ); 13C NMR (101 MHz, DMSO) δ 161.12
(d, J = 6.7 Hz, C, benzoxazole), 149.97 (Ph), 148.70 (Ph), 135.57
(d, J = 12.7 Hz, Ph), 134.46 (d, J = 7.0 Hz, Ph), 133.68 (Ph),
133.27 (d, J = 6.8 Hz, Ph), 132.67 (Ph), 131.11 (Ph), 130.15 (d, J
= 11.7 Hz, Ph), 129.37 (Ph), 128.61 (Ph), 128.56 -127.73 (m),
126.64 (Ph), 124.44 (Ph), 116.67 (Ph), 112.42 (Ph), 35.43
4: 70 % Isolated yield (yellow solid): FT-IR (KBr) : 2970 (s),
1609 (m), 1497 (s), 1481 (w), 1402 (w), 1346 (m), 1234 (m),
1099 (w), 1067 (w), 1019 (w), 828 (s), 749 (m), 549 (s); 1H NMR
(400 MHz, DMSO) δ 8.31 (d, J = 15.3 Hz, 1H, CH, imidazole),
8.25 (d, J = 7.8 Hz, 1H, Ph), 8.07-7.97 (m, 2H, Ph), 7.94 - 7.89
(m, 2H, , Ph), 7.86 (t, J = 7.7 Hz, 1H, Ph), 7.70 (dd, J = 8.8, 1.9
Hz, 1H, Ph), 7.62 (dd, J = 12.7, 2.0 Hz, 1H, Ph), 7.28 (d, J = 7.3
Hz, 1H, Ph), 7.23 (t, J = 7.3 Hz, 1H, Ph), 7.17 (t, J = 7.3 Hz, 1H,
Ph), 6.79 (d, J = 7.6 Hz, 1H, CH, imidazole), 5.84 (d, J = 16.4 Hz,
1H, CH2), 5.63 (d, J = 16.4 Hz, 1H, CH2), 2.36 (s, 3H, CH3), 1.36
(s, 9H, Ph-C(CH3)3), 1.31 (s, 3H, H, Cp*), 1.27 (s, 12H, H, Cp*);
13C NMR (101 MHz, DMSO) δ 163.43 (C, benzoxazole), 158.31
(C, imidazole), 149.04 (Ph), 148.53 (Ph), 139.02 (Ph), 137.87 (C,
imidazole), 136.18 (Ph), 135.36 (Ph), 134.94 (Ph), 134.03 (Ph),
130.54 (Ph), 129.58 (d, J = 5.8 Hz, C, imidazole), 127.76 (Ph),
127.31 -126.01 (Ph), 125.99 (Ph), 125.68 (Ph), 120.81 (Ph),
119.06 (Ph), 111.82 (Ph), 91.56 (d, J = 10.9 Hz, Ph), 55.33 (Ph),
52.37 (Ph), 35.43 (C(CH3)3), 31.76 (C(CH3)3), 19.27 (CH2), 8.93
(CH3), 8.71 (C, Cp*); 31P NMR (162 MHz, DMSO) δ-144.19
1
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins