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Dalton Transactions
Page 13 of 17
Journal Name
ARTICLE
(2C, CH), 100.34 (1C, CH), 28.34 (2C, CH3). Elemental Analysis: CH), 121.15 (1C, CH), 121.12 (1C, CH), 120.96 (1CV,ieCwHA)r,tic1le1O8n.l7in4e
DOI: 10.1039/C6DT01817C
calculated for C51H39IrN6O2 ∙ 1 C6H14: C, 65.43; H, 5.11; N, 8.03. (1C, CH), 118.71 (1C, CH), 118.42 (1C, CH), 118.29 (1C, CH),
Found: C, 65.10; H, 4.89; N, 7.91. Exact mass (MALDI) ‐ m/z: 38.45 (1C, CH2). Elemental Analysis: calculated for C46H34IrN5 ∙
960.2776 for [M]+ with (193Ir).
C3H6O: C, 64.88; H, 4.44; N, 7.72. Found: C, 64.75; H, 4.21; N,
General procedure for the synthesis of compounds 7.59. Exact mass (MALDI) ‐ m/z: 849.2443 for [M]+ with (193Ir).
[Ir(ppy)2( )], [Ir(ppy)2( )] and [Ir(ppy)2( )]. [Ir(ppy)2(3)]. Purification by column chromatography:
1
2
3
[Ir(ppy)2Cl]2 (150 mg, 0.14 mmol) and AgOTf (108 mg, 0.42 alumina/CH2Cl2 (Rf = 0.7). [Ir(ppy)2(
3)] was obtained as an
mmol) were dissolved in degassed acetone (8 mL) and refluxed orange powder (50 mg, 23%).
under nitrogen for 2 h. The solution was cooled to room 1H NMR (300 MHz, CDCl3): δ 8.71 (dd,
J
= 5.7, 0.7, 2H), 7.98–
temperature and gravity‐filtered to remove AgCl. The filtrate 7.89 (m, 6H), 7.83 (ddd, J= 8.1, 7.4, 1.5, 2H), 7.62 (dd, = 7.7,
was refluxed under nitrogen (55 °C) for 1 h and added to a 1 h 1.0, 2H), 7.59–7.47 (m, 3H), 7.33 (d, J= 8.9, 2H), 7.27 (ddd, J=
refluxed solution of the corresponding ligand or (0.56 7.2, 5.8, 1.4, 2H), 6.86 (td, = 7.5, 1.2, 2H), 6.74 (td, = 7.4, 1.3,
mmol) and NEt3 (147 µL, 1.05 mmol) in degassed acetone (4 2H), 6.33 (dd,
= 7.6, 0.9, 2H), 1.61 (s, 6H). 13C NMR (75 MHz,
mL). The resulting solution was refluxed overnight (55 °C) CDCl3): δ 182.99 (2C, Cquat.), 168.35 (2C, Cquat.), 152.33 (1C,
J
1,
2
3
J
J
J
under nitrogen. After removing the solvent, the residue was
purified by column chromatography.
C
quat.), 150.74 (1C, Cquat.), 147.72 (2C, CH), 147, 63 (2C, Cquat.),
146.15 (1C, Cquat.), 144.26 (2C, Cquat.), 136.50 (2C, CH), 132.69
[Ir(ppy)2(1)]. Purification by column chromatography: (4C, CH), 130.44 (1C, CH), 128.65 (2C, CH), 128.62 (2C, CH),
silica/CH2Cl2 (Rf = 0.8). [Ir(ppy)2(1)] was obtained as an orange 123.45 (2C, CH), 122.61 (2C, CH), 122.33 (2C, CH), 120.88 (2C,
powder (120 mg, 50%).
CH), 120.19 (2C, CH), 118.03 (2C, CH), 114.56 (1C, Cquat.), 29.18
(2C, CH3). Elemental Analysis: calculated for C39H31IrN4O2: C,
1H NMR (500 MHz, CDCl3): δ 8.07 (d,
J
= 5.0, 1H), 7.93 (d,
= 8.5, 2H), 7.78 (m, 3H), 60.06; H, 4.01; N, 7.18. Found: C, 59.85; H, 3.84; N, 7.05. Exact
= 5.9, 1H), 7.62 (m, 3H), 7.54–7.44 (m, 5H), 7.12 (d,
mass (MALDI) ‐ m/z: 780.2056 for [M]+ with (193Ir).
= 7.1, 1H), 6.93 (m, 8H), 6.70 (d, = 4.5, 2H), 6.63 (d, = 5.6, [Ir(Fppy)2(1)]. [Ir(Fppy)2Cl]2 (150 mg, 0.12 mmol) and AgOTf (95
1H), 6.47 (d,
= 7.1, 1H), 4.98 (s, 2H). 13C NMR (126 MHz, mg, 0.37 mmol) were dissolved in degassed acetone (8 mL)
CDCl3): δ 178.38 (1C, Cquat.), 175.06 (1C, Cquat.), 170.59 (1C, and refluxed under nitrogen for 2 h. The solution was cooled
quat.), 168.12 (1C, Cquat.), 167.98 (1C, Cquat.), 161.55 (1C, Cquat.), to room temperature and gravity‐filtered to remove AgCl. The
159.14 (1C, Cquat.), 153.35 (1C, CH), 152.91 (1C, Cquat.), 151.34 filtrate was refluxed under nitrogen for 1 h and added to a 1 h
(1C, CH), 147.88 (1C, CH), 146.87 (1C, Cquat.), 145.49 (1C, Cquat.), refluxed solution of (180 mg, 0.49 mmol) and NEt3 (130 µL,
J
=
6.7, 2H), 7.90 (d,
7.69 (d,
J = 7.7, 2H), 7.86 (d, J
J
J
J
J
J
C
1
144.84 (1C, Cquat.), 142.32 (1C, Cquat.), 137.24 (1C, CH), 137.22 0.93 mmol) in degassed acetone (4 mL). The resulting solution
(1C, Cquat.), 136.62 (1C, CH), 135.61 (1C, CH), 134.15 (1C, CH), was refluxed overnight under nitrogen. After removing the
132.81 (1C, CH), 130.59 (1C, CH), 130.36 (1C, CH), 130.07 (1C, solvent, the residue was purified by column chromatography:
CH), 129.76 (1C, CH), 129.13 (2C, CH), 124.66 (2C, CH), 124.50 silica/CH2Cl2 (Rf = 0.8). [Ir(Fppy)2(1)] was obtained as a light
(1C, CH), 124.21 (1C, CH), 124.11 (1C, CH), 122.60 (2C, CH), orange powder (92 mg, 40%).
122.45 (1C, CH), 122.13 (1C, CH), 121.29 (1C, CH), 120.98 (1C, 1H NMR (300 MHz, CDCl3): δ 8.22 (t,
J
= 9.1, 2H), 8.04 (dd,
CH), 120.68 (1C, CH), 119.18 (1C, CH), 119.01 (1C, CH), 118.67 5.8, 1.0, 1H), 7.98 (d, J=8.16, 1H), 7.95–7.88 (m, 5H), 7.81 (d,
(1C, CH), 118.48 (1C, CH), 115.44 (2C, CH), 71.04 (1C, CH2). = 8.1, 1H), 7.70 (td,
Elemental Analysis: calculated for C46H34IrN5O: C, 63.87; H, (dd, = 8.0, 1.8, 1H), 7.06–6.97 (m, 3H), 6.93 (d,
3.96; N, 8.10. Found: C, 64.43; H, 4.23; N, 7.60. Exact mass 6.77 (ddd, = 6.9, 6.0, 1.3, 1H), 6.76 (ddd, = 7.1, 5.9, 1.3, 1H)
(MALDI) ‐ m/z: 865.2393 for [M]+ with (193Ir).
6.52–6.42 (m, 2H), 6.05 (dd, = 7.5, 2.3, 1H), 5.84 (dd, = 9.2,
[Ir(ppy)2(
)]. Purification by column chromatography: 2.3, 1H), 5.06 (s, 2H). 13C NMR (75 MHz, CDCl3): δ 180.51 (1C,
J
=
J
J
= 8.0, 1.5, 1H), 7.62–7.48 (m, 6H), 7.18
= 1.5, 1H),
J
J
J
J
J
J
2
silica/CH2Cl2 (Rf = 0.8). [Ir(ppy)2(2)] was obtained as an orange
Cquat.), 175.19 (1C, Cquat.), 167.75 (1C, Cquat.), 166.89 (d, J=8.1,
powder (100 mg, 42%).
1C, Cquat.), 164.87 (dd, J=10.1, J=257, 1C, Cquat.), 164.59 (d,
= 5.8, 0.9, 1H), 7.98 J=6.8, 1C, Cquat.), 163.84 (dd, J=12.4, J= 253, 1C, Cquat.), 162.78
1H NMR (300 MHz, CDCl3): δ 8.15 (dd,
J
(dd,
7.61–7.43 (m, 6H), 7.10 (d,
(d, = 1.3, 1H), 6.72 (dddd,
(m, 1H), 6.56 (dd,
= 7.4, 1.3, 1H), 3.80 (s, 2H). 13C NMR (75 146.88 (1C, Cquat.), 144.89 (1C, Cquat.), 137.76 (1C, Cquat.), 137.13
J
= 8.2, 1.5, 2H), 7.87–7.72 (m, 7H), 7.70–7.63 (m, 3H), (d, J= 6.0, 1C, Cquat.), 162.27 (dd, J=10.9, J=262, 1C, Cquat.),
= 8.4, 2H), 7.02–6.84 (m, 7H), 6.72 161.66 (dd, J=13.1, J=258, 1C, Cquat.), 161.26 (1C, Cquat.), 153.10
=7.1, 5.8, 2.4, 1.2, 1H), 6.63‐6.61 (1C, CH), 152.82 (1C, Cquat.), 150.90 (1C, CH), 147.68 (1C, CH),
J
J
J
J
MHz, CDCl3): δ 177.31 (1C, Cquat.), 175.10 (1C, Cquat.), 170.52 (1C, CH), 136.55 (1C, CH), 136.45 (1C, CH), 135.22 (1C, CH),
(1C, Cquat.), 167.85 (1C, Cquat.), 166.65 (1C, Cquat.), 159.40 (1C, 130.27 (1C, CH), 129.01 (2C, CH), 127.88 (1C, Cquat.), 126.41
C
quat.), 153.17 (1C, CH), 152.67 (1C, Cquat.), 151.22 (1C, Cquat.), (1C, Cquat. C11H6NF2), 124.63 (1C, CH, C6H3), 124.57 (2C, CH),
150.95 (1C, CH), 147.77 (1C, CH), 145.18 (1C, Cquat.), 144.62 122.80 (d, J= 21.3, 1C, CH, C5H4N(C11H6NF2)), 122.66 (1C, CH),
(1C, Cquat.), 142.58 (1C, Cquat.), 142.25 (1C, Cquat.), 137.89 (1C, 122.58 (d, J=19.0, 1C, CH), 122.51 (2C, CH), 122.29 (1C, CH),
CH), 136.75 (1C, CH), 135.40 (1C, CH), 134.63 (1C, Cquat.), 121.48 (1C, CH), 121.17 (1C, CH), 119.43 (1C, CH), 115.32 (2C,
133.90 (1C, CH), 132.57 (1C, CH), 130.96 (1C, CH), 130.60 (1C, CH),113.71 (d, J=14.1, 1C, CH), 111.93 (d, J=16.3, 1C, CH), 97.42
CH), 130.04 (1C, CH), 129.69 (1C, CH), 129.48 (1C, CH), 129.30 (pst, J=27.2, 1C, CH), 95.47 (pst, J=27.1, 1C, CH), 70.67 (1C,
(2C, CH), 129.10 (2C, CH), 124.13 (1C, CH), 123.98 (1C, CH), CH2). Elemental Analysis: calculated for C46H30F4IrN5O ∙ C3H6O:
123.91 (1C, CH), 123.19 (2C, CH), 122.77 (2C, CH), 121.86 (1C,
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