Organometallics
Article
2-F). HRMS (FABMS): calcd for (C54H39F2N4Ir)+: m/z 974.2767;
found m/z 974.276253.
(2:1), and a purple solid of Ir(ttp)(4-F−C6H4) 3e (13.5 mg, 0.0141
mmol, 74%), and Ir(ttp)C6H5 3a (<5%) was isolated. When the
solvent was changed to hexane/CH2Cl2 (1:1), a purple solid of
Ir(ttp)(2,5-F2−C6H3) 3f (<5%) was isolated.
Reaction between Ir(ttp)SiEt3 1a and 1,4-Difluorobenzenes
2d in Benzene with the Addition of 10 Equivalents of KOH at
150 °C. Benzene (0.9 mL) and 1,4-difluorobenzene (0.2 mL, 100
equiv) were added to a mixture of Ir(ttp)SiEt3 (18.7 mg, 0.019 mmol)
and KOH (10.8 mg, 0.190 mmol, 10 equiv). Then the mixture was
heated at 150 °C for 5 days. The crude product was purified by
column chromatography eluting with a mixture of hexane/CH2Cl2
(3:1), and a purple solid of Ir(ttp)SiEt3 1a (1.2 mg, 0.0012 mmol, 6%)
was recovered. Then the solvent was changed to hexane/CH2Cl2
(2:1), and a purple solid mixture of Ir(ttp)(4-F−C6H4) 3e (15.4 mg,
0.0161 mmol, 85%) and Ir(ttp)C6H5 3a (<5%) was isolated.
Reaction between Ir(ttp)SiEt3 1a and Fluorobenzenes 2a−
2g with the Addition of 10 Equivalents of KOH at 200 °C in
Solvent-Free Conditions. Gererature Procedure. The reaction of
Ir(ttp)SiEt3 1a with fluorobenzene (2a) at 200 °C with the addition of
10 equiv of KOH is described as a typical example. Fluorobenzene (0.9
mL, 500 equiv) was added to a mixture of Ir(ttp)SiEt3 (18.4 mg, 0.019
mmol) and KOH (10.6 mg, 0.190 mmol, 10 equiv), and the mixture
was degassed by the freeze−pump−thaw method (3 cycles). Then the
mixture was heated at 200 °C for 2 days. The crude product was
purified by column chromatography on alumina eluting with a mixture
of hexane/CH2Cl2 (2:1), and a purple solid mixture of Ir(ttp)C6H5 3a
(11.4 mg, 0.0122 mmol, 64%), Ir(ttp)(2-F−C6H4) 3b (<5%),
Ir(ttp)(3-F−C6H3) 2d (3.2 mg, 0.0033 mmol, 18%), and Ir(ttp)(4-
F−C6H4) 3e (0.9 mg, 0.0009 mmol, 5%) were isolated. Ir(ttp)(2-F−
1
Ir(ttp)C6H5 3a, Rf = 0.35 (hexane/CH2Cl2 = 1:1). H NMR (C6D6,
400 MHz): δ 1.10 (d, 2 H, J = 8.0 Hz), 2.39 (s, 12 H), 4.89 (t, 2 H, J =
7.2 Hz), 5.23 (t, 1 H, J = 7.2 Hz), 7.19 (d, 4 H, J = 7.6 Hz), 7.33 (d, 4
H, J = 7.6 Hz), 7.87 (dd, 4 H, J = 1.6, 7.6 Hz), 8.14 (dd, 4 H, J = 1.6,
7.6 Hz), 8.80 (s, 8 H). 13C NMR (CDCl3, 100 MHz): δ 21.6, 95.2,
120.1, 123.2, 124.1, 127.5, 129.0, 131.5, 133.6, 134.2, 137.3, 138.7,
143.0. HRMS (FABMS): calcd for (C54H41N4Ir)+: m/z 938.2955;
found m/z 938.294798. When the solvent was changed to hexane/
CH2Cl2 (1:1), a purple solid of Ir(ttp)(2,5-F2−C6H3) 3f (<5%) was
isolated.
1
C6H4) 3b, Rf = 0.35 (hexane/CH2Cl2 = 1:1). H NMR (C6D6, 400
MHz): δ 0.79 (dd, 1 H, 4JHF = 7.4 Hz, J = 7.2 Hz), 2.38 (s, 12 H), 4.44
(ddd, 1 H, 3JHF = 10.5 Hz, J = 1.4, 8.6 Hz), 4.79 (t, 1 H, J = 7.6 Hz),
5.09 (td, 1 H, 4JHF = 5.6 Hz, J = 6.2 Hz), 7.20 (d, 4 H, J = 7.6 Hz), 7.32
(d, 4 H, J = 7.6 Hz), 7.96 (dd, 4 H, J = 1.6, 7.6 Hz), 8.13 (dd, 4 H, J =
1.6, 7.6 Hz), 8.85 (s, 8 H). 13C NMR (CD2Cl2, 100 MHz): δ 21.6,
81.7 (d, 2JCF = 26.6 Hz), 110.8 (d, 2JCF = 27.9 Hz), 119.2 (d, 4JCF = 2.4
Hz), 121.7 (d, 3JCF = 8.2 Hz), 123.7, 127.7, 127.8, 131.6, 133.9, 134.0
Reaction between Ir(ttp)SiEt3 1a and 1,4-Difluorobenzenes
2d in Benzene with the Addition of 10 Equivalents of KOH at
200 °C. Benzene (0.9 mL) and 1,4-difluorobenzene (0.2 mL, 100
equiv) were added to a mixture of Ir(ttp)SiEt3 (18.4 mg, 0.019 mmol)
and KOH (10.6 mg, 0.190 mmol, 10 equiv). Then the mixture was
heated at 200 °C for 3 days. The crude product was purified by
column chromatography, eluting with a mixture of hexane/CH2Cl2
(3:1), and a purple solid of Ir(ttp)SiEt3 1a (<5%) was recovered. Then
the solvent was changed to hexane/CH2Cl2 (2:1), and a purple solid
mixture of Ir(ttp)(4-F−C6H4) 3e (9.4 mg, 0.0098 mmol, 52%) and
Ir(ttp)C6H5 3a (5.2 mg, 0.0055 mmol, 29%) was isolated. When the
solvent was changed to hexane/CH2Cl2 (1:1), a purple solid of
Ir(ttp)(2,5-F2−C6H3) 3f (1.5 mg, 0.0015 mmol, 8%) was isolated.
Reaction between Ir(ttp)SiEt3 1a and 1,4-Difluorobenzenes
2d in Benzene-d6 with the Addition of KOH at 200 °C. Benzene-
d6 (0.9 mL) and 1,4-difluorobenzene (0.2 mL, 100 equiv) were added
to a mixture of Ir(ttp)SiEt3 (18.5 mg, 0.019 mmol) and KOH (10.6
mg, 0.190 mmol, 10 equiv). Then the mixture was heated at 200 °C
for 3 days. The crude product was purified by column chromatography
eluting with a mixture of hexane/CH2Cl2 (3:1), and a purple solid of
Ir(ttp)SiEt3 1a (6.4 mg, 0.0066 mmol, 34%) was recovered. Then the
solvent was changed to hexane/CH2Cl2 (2:1), and a purple solid
mixture of Ir(ttp)(4-F−C6H4) 3e (9.0 mg, 0.0094 mmol, 50%) and
Ir(ttp)C6D5 3a′ (1.2 mg, 0.0013 mmol, 6%) was isolated. When the
solvent was changed to hexane/CH2Cl2 (1:1), a purple solid of
Ir(ttp)(2,5-F2−C6H3) 3f (1.2 mg, 0.0012 mmol, 6%) was isolated.
Reaction between Ir(ttp)SiEt3 1a and 1,4-Difluorobenzenes
2d in Benzene with the Addition of 5 Equivalents of KOH at
150 °C. Benzene (0.8 mL) and 1,4-difluorobenzene (0.2 mL, 100
equiv) were added to a mixture of Ir(ttp)SiEt3 (17.8 mg, 0.018 mmol)
and KOH (5.1 mg, 0.090 mmol, 5 equiv). Then the mixture was
heated at 150 °C for 5 days. The crude product was purified by
column chromatography eluting with a mixture of hexane/CH2Cl2
(3:1), and a purple solid of Ir(ttp)SiEt3 1a (3.1 mg, 0.0032 mmol,
17%) was recovered. Then the solvent was changed to hexane/CH2Cl2
(2:1), and a purple solid of Ir(ttp)(4-F−C6H4) 3e (10.6 mg, 0.0111
mmol, 61%) and Ir(ttp)C6H5 3a (<5%) was isolated. When the
solvent was changed to hexane/CH2Cl2 (1:1), a purple solid of
Ir(ttp)(2,5-F2−C6H3) 3f (1.9 mg, 0.0020 mmol, 11%) was isolated.
Reaction between Ir(ttp)SiEt3 1a and 1,4-Difluorobenzenes
2d in Benzene with the Addition of 20 Equivalents of KOH at
150 °C. Benzene (0.9 mL) and 1,4-difluorobenzene (0.2 mL, 100
equiv) were added to a mixture of Ir(ttp)SiEt3 (18.6 mg, 0.019 mmol)
and KOH (21.4 mg, 0.380 mmol, 20 equiv). Then the mixture was
heated at 150 °C for 4 days. The crude product was purified by
column chromatography eluting with a mixture of hexane/CH2Cl2
(3:1), and a purple solid of Ir(ttp)SiEt3 1a was recovered in trace
amount (<5%). Then the solvent was changed to hexane/CH2Cl2
3
1
(d, JCF = 11.6 Hz), 134.5, 137.8, 139.0, 143.4, 163.9 (d, JCF = 240.1
Hz). 19F NMR (CD2Cl2, 376 MHz): δ −45.55 (dt, 1 F, 4JFH = 5.3 Hz,
3JFH = 10.5 Hz, 2-F). HRMS (FABMS): calcd for (C54H40FN4Ir)+: m/
z 956.2861; found m/z 956.284725. A single crystal for X-ray analysis
was grown fron CH2Cl2/hexane. Ir(ttp)(3-F−C6H4) 3d, Rf = 0.35
(hexane/CH2Cl2 = 1:1). 1H NMR (C6D6, 400 MHz): δ 0.85 (d, 1 H, J
= 8.4 Hz), 0.88 (ddd, 1 H, 3JHF = 12.0 Hz, J = 1.6, 2.0 Hz), 2.39 (s, 12
H), 4.65 (dd, 1 H, 3JHF = 15.2 Hz, J = 8.0 Hz), 4.94 (td, 1 H, 4JHF = 2.4
Hz, J = 8.4 Hz), 7.18 (d, 4 H, J = 7.6 Hz), 7.32 (d, 4 H, J = 7.6 Hz),
7.90 (dd, 4 H, J = 2.0, 7.6 Hz), 8.14 (dd, 4 H, J = 2.0, 7.8 Hz), 8.82 (s,
8 H). 13C NMR (CDCl3, 100 MHz): δ 21.6, 98.2, 106.5 (d, 2JCF = 20.8
Hz), 115.3 (d, 2JCF = 19.6 Hz), 123.1 (d, 3JCF = 8.0 Hz), 123.8, 124.9,
1
127.5, 127.6, 131.6, 133.6, 134.2, 137.4, 138.7, 142.9, 155.0 (d, JCF
=
=
4
243.1 Hz). 19F NMR (C6D6, 376 MHz): δ −54.19 (ddd, 1 F, JFH
3
3.4 Hz, JFH = 12.0, 15.8 Hz, 3-F). HRMS (FABMS): calcd for
(C54H40FN4Ir)+: m/z 956.2861; found m/z 956.286859.
Reaction between Ir(ttp)SiEt3 1a and 1,2-Difluorobenzenes
2b with the Addition of 10 Equivalents of KOH at 200 °C in
Solvent-Free Conditions. 1,2-Difluorobenzene (1.0 mL, 500 equiv)
was added to a mixture of Ir(ttp)SiEt3 (19.4 mg, 0.020 mmol) and
KOH (11.2 mg, 0.200 mmol, 10 equiv). Then the mixture was heated
at 200 °C for 2 days. The crude product was purified by column
chromatography eluting with a mixture of hexane/CH2Cl2 (2:1), and a
purple solid of Ir(ttp)(2-F−C6H4) 3b (1.1 mg, 0.0012 mmol, 6%) was
isolated. Then the solvent was changed to hexane/CH2Cl2 (1:1), and a
purple solid of Ir(ttp)(2,3-F2−C6H3) 3c (17.2 mg, 0.0177 mmol, 89%)
1
was isolated. Rf = 0.25 (hexane/CH2Cl2 = 1:1). H NMR (C6D6, 400
5
4
MHz): δ 0.53 (dddd, 1 H, JHF = 1.4 Hz, JHF = 6.8 Hz, J = 1.2, 6.8
5
4
Hz), 2.38 (s, 12 H), 4.54 (tdd, 1 H, JHF = 1.2 Hz, JHF = 6.2 Hz, J =
7.8 Hz), 4.93 (dddd, 1 H, 4JHF = 8.8 Hz, 3JHF = 9.2 Hz, J = 1.3, 7.9 Hz),
7.19 (d, 4 H, J = 7.2 Hz), 7.30 (d, 4 H, J = 7.6 Hz), 7.96 (dd, 4 H, J =
1.6, 7.6 Hz), 8.11 (dd, 4 H, J = 1.6, 8.6 Hz), 8.86 (s, 8 H). 13C NMR
(CD2Cl2, 100 MHz): δ 21.6, 87.5 (d, 2JCF = 23.6 Hz), 108.3 (d, 2JCF
=
17.3 Hz), 118.1 (dd, 3JCF = 6.6 Hz, 4JCF = 3.1 Hz), 123.5, 127.6, 127.8,
3
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129.2 (dd, JCF = 11.0 Hz, JCF = 3.2 Hz), 131.5, 134.0, 134.4, 137.7,
1
2
139.1, 143.3, 144.7 (dd, JCF = 242.9 Hz, JCF = 18.1 Hz), 152.4 (dd,
1JCF = 239.4 Hz, JCF = 10.2 Hz). 19F NMR (CD2Cl2, 376 MHz): δ
2
−79.80 (ddd, 1 F, 4JFH = 5.6 Hz, 3JFH = 10.0 Hz, 3JFF = 21.4 Hz, 3-F),
−73.04 (dt, 1F, 4JFH = 5.3 Hz, 3JFF = 21.8 Hz, 2-F). HRMS (FABMS):
calcd for (C54H39F2N4Ir)+: m/z 974.2767; found m/z 974.278921.
Reaction between Ir(ttp)SiEt3 1a and 1,3-Difluorobenzenes
2c with the Addition of 10 Equivalents of KOH at 200 °C in
Solvent-Free Conditions. 1,3-Difluorobenzene (1.0 mL, 500 equiv)
was added to a mixture of Ir(ttp)SiEt3 (18.8 mg, 0.019 mmol) and
G
dx.doi.org/10.1021/om5005594 | Organometallics XXXX, XXX, XXX−XXX