Organometallics
Article
5
2
1.41, H 6.55, N 6.66. Found: C 51.43, H 6.52, N 6.68. IR (nujol)
arom), 128.4 (CH arom), 127.8 (2 CH arom), 127.2 (2 CH arom),
125.6 (CH arom), 120.9 (d, JCP = 2 Hz, CH arom), 120.7 (d, JCP = 7
Hz, CH arom), 120.0 (CH arom), 119.4 (d, JCP = 3 Hz, CH arom),
−
1 1
101 (νIrH) cm . H NMR (500 MHz, C D ) δ 6.83 (m, 3H, 2 H
6
6
3
arom Mes + H arom Py), 6.60 (d, J = 7.5 Hz, 1H, H arom Py),
HH
3
6
6
.56 (s, 1H, H arom NHC), 6.40 (d, J = 7.3 Hz, 1H, H arom Py),
76.8 (CHN), 75.4 (CHOIr), 39.6 (d, JCP = 21 Hz, C(CH )), 36.8 (d,
HH
3
2
.34 (s, 1H, H arom NHC), 4.72 (s, 2H, CH N), 3.03 (d, J = 7.9
JCP = 7 Hz, CH P), 31.9 (d, J = 23 Hz, C(CH )), 30.6 (d, J = 3
2
HP
2
CP
3
CP
3
Hz, 2H, CH P), 2.30 (s, 6H, 2 CH ), 2.11 (s, 3H, CH ), 1.29 (d, J
Hz, 3 C(CH )), 29.5 (d, J = 5 Hz, 3 C(CH )), 21.0 (CH ), 19.1
2
3
3
HP
3
CP
3
3
2
2
=
12.0 Hz, 18H, 2 C(CH ) ), −10.14 (dd, J = 15.6 Hz, J = 5.4
(CH ), 18.2 (CH ).
Diagnostic NMR spectroscopy data for complex 8a : H NMR
3
3
HP
HH
3
3
2
2
m
1
Hz, 2H, 2 IrH cis to Py), −20.03 (dt, J = 13.8 Hz, J = 5.4 Hz,
HP
HH
3
1
1
2
2
1
H, IrH trans to Py). P{ H} NMR (202 MHz, C D ) δ 76.3.
C{ H} NMR (126 MHz, C D ) δ 178.8 (d, J = 113 Hz, C-2
(500 MHz, THF-d ) δ −20.06 (dd, J = 13.7 Hz, J = 7.4 Hz,
6
6
8
HP
HH
13
1
2 2
HP
1H, IrH trans to Py), −24.11 (dd, J = 18.5 Hz, J = 7.4 Hz, 1H,
6
6
CP
HH
31 1
NHC), 166.8 (d, JCP = 5 Hz, C arom), 154.7 (C arom), 138.9 (C
arom), 137.2 (C arom), 136.4 (2 C arom), 132.1 (CH arom), 128.9
IrH cis to Py). P{ H} NMR (162 MHz, THF-d
8
) δ 76.1.
q
q
q
M
m
Complexes 8b /8b . In a J. Young valved NMR tube, a solution
q
q
(2 CH arom), 120.0 (CH arom), 119.8 (d, JCP = 8 Hz, CH arom),
of 4a (0.010 g, 0.015 mmol) in THF-d (0.5 mL) was treated with
8
1
5
19.1 (d, JCP = 4 Hz, CH arom), 118.6 (d, JCP = 3 Hz, CH arom),
9.8 (CH N), 41.0 (d, J = 19 Hz, CH P), 33.2 (d, J = 17 Hz, 2
KHMDS (0.004 g, 0.020 mmol) and p-bromobenzaldehyde (0.004 g,
0.022 mmol). The resulting solution was analyzed by NMR
spectroscopy.
2
CP
2
CP
C(CH )), 29.9 (d, J = 5 Hz, 6 C(CH )), 21.2 (CH ), 19.6 (2 CH ).
3
CP
3
3
3
M
1
Complexes 6b and 7. Tetrahydrofuran (8 mL) was added to an
:2 mixture of complexes 4b and 5 (0.078 g, 0.12 mmol) and NaH
0.057 g, 2.39 mmol), and the resulting suspension was stirred
NMR spectroscopy data for complex 8b : H NMR (500 MHz,
3
3
8
(
THF-d ) δ 7.78 (dd, JHH = 8.0 Hz, JHH = 8.0 Hz, 1H, H arom Py),
8
3
3
7.54 (d, JHH = 8.0 Hz, H arom Py), 7.44 (d, JHH = 8.1 Hz, H arom
Py), 7.36 (d, JHH = 8.1 Hz, 2H, 2 H arom p-BrPh), 7.19 (d, JHH =
3
3
overnight at room temperature. The solid was filtered through a short
pad of Celite, and the solvent was evaporated. The obtained yellow
solid was washed with pentane (2 × 8 mL) and dried under a vacuum
8.1 Hz, 2H, 2 H arom p-BrPh), 6.95 (s, 1H, H arom), 6.81 (s, 2H, 2
H arom), 6.66 (s, 1H, H arom), 5.62 (s, 1H, CHN), 4.87 (s, 1H,
2
2
(
0.079 g, 88%). Compounds 6b and 7 were obtained in an 8:2 ratio.
CHOIr), 3.61 (d, JHH = 15.6 Hz, JHP = 8.8 Hz, 1H, CHHP), 2.95
2
2
Anal. Calcd (%) for 0.8 C H IrN P + 0.2 C H IrN P: C 50.60, H
(dd, JHH = 15.6 Hz, JHP = 6.7 Hz, 1H, CHHP), 2.28 (s, 3H, CH ),
), 1.74 (s, 3H, CH
C(CH ), 1.03 (d, JHP = 12.3 Hz, 9H, C(CH
3
2
6
39
3
26 41
3
3
6
.43, N 6.81. Found: C 50.23, H 6.78, N 6.46. IR (nujol) 2106 (νIrH)
2.18 (s, 3H, CH
3
3
), 1.22 (d, JHP = 12.1 Hz, 9H,
−
1
3
2
cm .
NMR spectroscopy data for complex 6b: H NMR (400 MHz,
THF-d ) δ 7.81 (s, 2H, 2 H arom Xyl), 7.56 (dd, J = 7.6 Hz, J
3
)
3
3
)
3
), −19.39 (dd, JHP
1
2
2
= 14.2 Hz, JHH = 7.8 Hz, 1H, IrH trans to Py), −24.48 (dd, JHP
=
3
3
2
31
1
18.4 Hz, JHH = 7.8 Hz, 1H, IrH cis to Py). P{ H} NMR (202 MHz,
8
HH
HH
3
13
1
=
7.6 Hz, 1H, H arom Py), 7.33 (d, J = 8.1 Hz, 1H, H arom Py),
THF-d
= 4 Hz, C
arom), 138.0 (C
8
) δ 75.6. C{ H} NMR (101 MHz, THF-d
arom), 158.7 (C arom), 149.8 (C arom), 138.6 (C
arom), 136.7 (C arom), 136.3 (C arom), 136.2
8
) δ 166.9 (d, JCP
HH
3
7
7
.29 (s, 1H, H arom NHC), 7.22 (d, J = 7.5 Hz, 1H, H arom Py),
.18 (s, 1H, H arom NHC), 6.88 (s, 1H, H arom Xyl), 5.13 (s, 2H,
q
q
q
q
HH
q
q
q
2
CH N), 3.35 (d, J = 8.1 Hz, 2H, CH P), 2.34 (s, 6H, 2 CH ), 1.31
(CH arom), 130.4 (2 CH arom), 130.0 (2 CH arom), 129.2 (CH
arom), 128.6 (CH arom), 121.1 (m, 2 CH arom), 120.3 (CH arom),
2
HP
2
3
3
2
(
d, J = 12.0 Hz, 18H, 2 C(CH ) ), −10.62 (dd, J = 16.0 Hz,
HP
3
3
HP
2
2 2
JHH = 5.1 Hz, 2H, 2 IrH), −20.37 (dt, J = 14.6 Hz, J = 5.0 Hz,
1
120.0 (CH arom), 119.4 (C
39.8 (d, JCP = 21 Hz, C(CH )), 36.9 (d, JCP = 7 Hz, CH
CP = 23 Hz, C(CH )), 30.8 (d, JCP = 3 Hz, 3 C(CH )), 29.6 (d, JCP
4 Hz, 3 C(CH )), 21.2 (CH ), 19.2 (CH ), 18.3 (CH ) ppm; signal
q
arom), 76.5 (CHN), 75.0 (CHOIr),
HP
HH
H, IrH). 31P{ H} NMR (162 MHz, THF-d ) δ 77.3. C{ H} NMR
1
13
1
P), 32.1 (d,
8
3
2
(101 MHz, THF-d ) δ 177.8 (d, J = 113 Hz, C-2 NHC), 166.3 (d,
J
3
3
=
8
CP
JCP = 5 Hz, C arom), 154.5 (C arom), 142.6 (C arom), 136.2 (2 C
3
3
3
3
q
q
q
q
arom), 132.7 (CH arom), 127.1 (CH arom), 124.8 (2 CH arom),
19.6 (m, 2 CH arom), 119.2 (d, JCP = 4 Hz, CH arom), 119.1 (CH
arom), 59.3 (CH N), 40.3 (d, J = 20 Hz, CH P), 32.6 (d, J = 17
of the C2-NHC carbon could not be detected due to the low
M
1
solubility of complex 8b . This signal was determined to appear at
1
13
176.0 ppm from the H− C HBQC experiment.
2
CP
2
CP
m
1
Hz, 2 C(CH )), 29.1 (d, J = 5 Hz, 6 C(CH )), 20.3 (2 CH ).
Diagnostic NMR spectroscopy data for complex 8b : H NMR
3
CP
3
3
1
2
2
NMR spectroscopy data for complex 7: H NMR (400 MHz, THF-
(500 MHz, THF-d
8
) δ −20.01 (dd, JHP = 14.0 Hz, JHH = 7.7 Hz,
2 2
3
3
d ) δ 7.78 (s, 2H, 2 H arom Xyl), 7.53 (dd, J = 7.5 Hz, J = 7.5
1H, IrH trans to Py), −24.34 (dd, JHP = 19.5 Hz, JHH = 7.7 Hz, 1H,
8
HH
HH
3
31
1
Hz, 1H, H arom Py), 7.39 (d, J = 7.4 Hz, 1H, H arom Py), 7.31 (s,
IrH cis to Py). P{ H} NMR (162 MHz, THF-d ) δ 76.1.
8
HH
3
1H, H arom NHC), 7.36 (s, 1H, H arom NHC), 7.12 (d, J = 7.5
Complex 9. A solution of 4a (0.070 g, 0.105 mmol) in THF (5
mL) was treated with KHMDS (0.022 g, 0.110 mmol) and
benzaldehyde (32 μL, 0.315 mmol). The suspension was filtered
through a short pad of Celite. Water (50 μL) was added, and the
resulting solution was heated to 60 °C for 6 h. The reaction mixture
HH
Hz, 1H, H arom Py), 6.68 (s, 1H, H arom Xyl), 4.57 (s, 2H, CH N),
2
3
3
3.99 (t, J = 8.5 Hz, 2H, CH CH ), 3.76 (t, J = 8.7 Hz, 2H,
HH 2 2 HH
2
CH CH ), 3.35 (d, J = 8.1 Hz, 2H, CH P), 2.28 (s, 6H, 2 CH ),
1
Hz, J = 5.0 Hz, 2H, 2 IrH), −20.65 (dt, J = 14.2 Hz, J = 5.0
Hz, 1H, IrH). P{ H} NMR (162 MHz, THF-d ) δ 76.5.
2
2
HP
2
3
3
2
.23 (d, J = 12.9 Hz, 18H, 2 C(CH ) ), −10.56 (dd, J = 17.6
HP
3
3
HP
2
2
2
was brought to dryness, and the residue was washed with Et
mL) and cold THF (3 mL). Yellow solid (0.047 g, 60%). Anal. Calcd
(%) for C34 P: C 54.38, H 6.04, N 5.60. Found: C 54.42, H
5.96, N 5.36. IR (nujol) 1601 (νas, COO) cm . H NMR (400 MHz,
O (3 × 5
HH
HP
HH
2
31
1
8
M
m
Complexes 8a /8a . In a J. Young valved NMR tube, a solution
H45IrN O
3 2
−
1 1
of 4a (0.020 g, 0.030 mmol) in THF-d (0.5 mL) was treated with
KHMDS (0.008 g, 0.039 mmol) and benzaldehyde (6.0 μL, 0.060
mmol). The resulting solution was analyzed by NMR spectroscopy.
8
3
3
CD Cl ) δ 7.81 (d, JHH = 7.0 Hz, 2H, 2 H arom), 7.69 (t, JHH = 7.7
2 2
3
Hz, 1H, H arom), 7.45 (d, JHH = 7.6 Hz, 1H, H arom), 7.22 (m, 5H,
M
1
NMR spectroscopy data for complex 8a : H NMR (500 MHz,
5 H arom), 7.01 (s, 1H, H arom), 6.85 (s, 2H, 2 H arom), 6.13 (d,
3
3
2
2
THF-d ) δ 7.74 (t, J = 7.6 Hz, 1H, H arom), 7.62 (t, J = 7.4
JHH = 14.6 Hz, 1H, CHHN), 4.85 (d, JHH = 14.6 Hz, 1H, CHHN),
8
HH
HH
2
2
2
Hz, 1H, H arom), 7.53 (m, H arom), 7.43 (m, 2 H arom), 7.04 (m,
H, 2 H arom), 6.91 (m, 2H, 2 H arom), 6.80 (s, 1H, H arom), 6.75
s, 1H, H arom), 6.59 (s, 1H, H arom), 5.64 (s, 1H, CHN), 4.90 (s,
3.56 (dd, J = 16.7 Hz, J = 8.8 Hz, 1H, CHHP), 2.81 (dd, J
= 16.7 Hz, J = 7.5 Hz, 1H, CHHP), 2.33 (s, 3H, CH ), 2.31 (s,
HP 3
3H, CH ), 1.82 (s, 3H, CH ), 1.18 (d, J = 12.5 Hz, 18H, 2
HH HP HH
2
2
3
(
1
2
3 3 HP
2
2
2
2
H, CHOIr), 3.61 (d, J = 15.5 Hz, J = 8.9 Hz, 1H, CHHP),
.95 (dd, J = 15.5 Hz, J = 6.7 Hz, 1H, CHHP), 2.28 (s, 3H,
C(CH ) ), −19.91 (dd, J = 14.4 Hz, J = 6.7 Hz, 1H, IrH trans
HH
HP
3
3
HP
HH
2
2
2 2
to Py), −26.85 (dd, J = 17.1 Hz, J = 6.7 Hz, 1H, IrH cis to Py).
HH
HP
HP
HH
3
31 1 13 1
CH ), 2.21 (s, 3H, CH ), 1.74 (s, 3H, CH ), 1.23 (d, J = 12.1 Hz,
P{ H} NMR (122 MHz, CD Cl ) δ 63.0. C{ H} NMR (101
3
3
3
HP
2 2
3
9
H, C(CH ) ), 1.05 (d, J = 12.1 Hz, 9H, C(CH ) ), −19.39 (dd,
MHz, CD Cl ) δ 174.7 (d, J = 116 Hz, C-2 NHC), 171.0 (Ir-
2 2 CP
3
3
HP
3
3
2
2
2
JHP = 14.2 Hz, J = 7.8 Hz, 1H, IrH trans to Py), −24.33 (dd, J
=
CO Ph), 167.3 (C arom), 156.5 (C arom), 138.9 (C arom), 138.4
HH
HP
2 q q q
2
31
1
18.2 Hz, J = 7.8 Hz, 1H, IrH cis to Py). P{ H} NMR (162
(C arom), 138.0 (C arom), 137.2 (C arom), 135.7 (CH arom + C
q q q q
HH
1
3
1
MHz, THF-d ) δ 75.5. C{ H} NMR (101 MHz, THF-d ) δ 176.7
arom), 129.7 (2 CH arom), 129.0 (CH arom), 128.9 (CH arom),
128.1 (CH arom), 127.4 (2 CH arom), 121.9 (CH arom), 121.6 (d,
JCP = 8 Hz, CH arom), 120.4 (CH arom), 119.9 (CH arom), 56.8
(CH N), 39.1 (d, J = 22 Hz, C(CH )), 36.8 (d, J = 9 Hz, CH P),
8
8
(
(
1
d, JCP = 119 Hz, C-2 NHC), 166.6 (d, JCP = 5 Hz, C arom), 158.9
C arom), 150.4 (C arom), 138.5 (C arom), 137.8 (C arom),
36.7 (C arom), 136.2 (C arom), 135.9 (CH arom), 129.2 (CH
q
q
q
q
q
q
q
2
CP
3
CP
2
1
323
Organometallics 2021, 40, 1314−1327