H. Zhang et al. / Journal of Molecular Catalysis A: Chemical 411 (2016) 337–343
339
Table 1
Crystal data and structure refinement for Ir-L1a, Ir-L1b, Ir-L2a and Ir-L2b.
Ir-L1a.CH2Cl2
Ir-L1b.H2O
Ir-L2a
Ir-L2b
Empirical formula
C37H27Ir1N4O1P2.CH2Cl2
882.69
Monoclinic
P21/c
13.0624(7)
17.2838(10)
16.2701(9)
90
108.816(2)
90
3477.0(3)
4
1.686
4.123
173(2)
C37H28Cl1Ir1N4O1P2.H2O1
852.22
Orthorhombic
Pbcn
26.2223(5)
18.4901(4)
28.9516(6)
90
C39H34Ir1N4O2P2.2(CF3SO3)
C39H34Cl1Ir1N4O1P2.2(CF3SO3)
1162.43
Triclinic
Formula weight
Crystal system
Space group
a (Å)
1142.98
Orthorhombic
Pbca
16.1818(11)
20.7304(15)
26.5775(18)
90
P-1
12.8635(4)
13.8201(4)
13.9595(4)
76.8250(10)
79.0570(10)
68.5560(10)
2233.47(11)
2
1.728
3.293
296(2)
0.71073
26183
7811 (0.0333)
0.0306
0.0896
1148
b (Å)
c (Å)
˛ (0)
ˇ (0)
90
90
90
90
ꢂ (0)
V (Å3)
14037.3(5)
16
1.609
4.010
296(2)
0.71073
159026
12367 (0.0670)
0.0354
0.0835
6688
8915.6(11)
8
1.703
Z
dcalc (g cm−3
)
ꢃ (Mo-K␣) (mm−1
T (K)
)
3.241
296(2)
0.71073
98932
7838 (0.0881)
0.0430
0.1112
4520
ꢄ (A)
Total reflections
Unique reflections (Rint
R1 [I > 2ꢁ(I)]
wR2 (all data)
0.71073
40121
6129 (0.0911)
0.0333
0.0695
1736
)
F(000)
Goodness-of-fit on F2
1.027
1.066
1.037
1.092
center complex-cation, the signals of 1H NMR and 31P NMR of Ir-L2a
attributed to ligand L2 were broadened to flatness. CHN-elemental
analysis (found): C 42.67, H 3.24, N 4.62 (calcd., C 43.08, H 2.98, N
4.90).
X-ray diffraction analysis was obtained by recrystallization from
CH2Cl2/n-hexane. 1H NMR (400 MHz, ı, ppm, CD2Cl2): ı = 7.56–7.61
(m, 8H, HPh), 7.34–7.43 (m, 14H, HPh), 7.27 (s, 2H, Himi), 6.78 (t,
J = 8 Hz, 1H, HPh), 6.70 (s, 1H, Himi), 6.68 (s, 1H, Himi). 31P NMR
(162 MHz, ı, ppm, CD2Cl2): ı = 11.69 (s, PPh2). 13C NMR (125 MHz,
ı, ppm, CD2Cl2): ı = 187.89 (t, J = 8.75 Hz, Ir-CO), 144.62 (t, J = 2.5 Hz,
Ir-complex upon coordination of L2 to [Ir(cod)Cl]2 (Ir-L2b)
Under nitrogen atmosphere, a solution of [Ir(cod)Cl]2 (33.6 mg,
0.05 mmol) in dry CH2Cl2 (2 mL) was stirred vigorously at room
temperature for about 10 min and then the atmospheric CO (in a
balloon) was introduced into the reaction mixture for 20 min. The
obtained mixture was then treated with a solution of L2 (90.7 mg,
0.1 mmol) in acetonitrile (5 mL) and was stirred vigorously for
about 4.5 h. Then diethyl ether was added to precipitate the yellow
solids, which were collected after dryness under vacuum with the
yield of 81% (94 mg). The sample suitable for X-ray diffraction anal-
ysis was obtained by recrystallization from acetonitrile/n-hexane.
1H NMR (400 MHz, ı, ppm, CD3CN): ı = 8.63 (t, J = 4 Hz, 1H, HPh),
8.05 (s, 2H, Himi), 7.82–7.49 (m, 25H, HPh + imi), 3.27 (s, 6H, NCH3).
31P NMR (162 MHz, ı, ppm, CD3CN): ı = 12.22 (s, PPh2). 13C NMR
(125 MHz, ı, ppm, CD3CN): ı = 167.49 (s, Ir-CO), 139.20 (t, J = 20 Hz,
C
Ar), 142.18 (t, J = 13.75 Hz, CAr), 135.87 (t, J = 42.5 Hz, CAr), 134.45
(s, CAr), 132.07 (t, J = 5 Hz, CAr), 131.29 (s, CAr), 130.24 (t, J = 26.25 Hz,
Ar), 128.53 (t, J = 6.25 Hz, CAr), 127.35 (s, CAr), 122.78 (s, CAr), 121.27
C
(s, CAr). CHN-elemental analysis (found): C 55.15, H 3.64, N 6.8
(calcd., C 55.70, H 3.41, N 7.02).
Ir-complex upon coordination of L1 to [Ir(cod)Cl]2 (Ir-L1b)
Ir-L1b. Under nitrogen atmosphere, a solution of [Ir(cod)Cl]2
(33.6 mg, 0.05 mmol) in dry CH2Cl2 (2 mL) was stirred vigorously
at room temperature for about 10 min. Then the atmospheric CO
(in a balloon) was introduced into the reaction mixture for 20 min.
Afterwards, the reaction mixture was treated with a solution of L1
(57.9 mg, 0.1 mmol) in dry CH2Cl2 (3 mL). The resultant mixture was
stirred for another 2.5 h and then n-hexane was added to precipitate
the yellow solids. The yellow solids were collected after dryness
under vacuum with the yield of 89% (74 mg). The sample suitable
for X-ray diffraction analysis was obtained by slow volatilization
from acetonitrile. 1H NMR (400 MHz, ı, ppm, CD3CN): ı = 8.49 (s,
1H, HPh), 8.28–8.33 (m, 4H, HPh), 7.68 (s, 2H, HPh), 7.44–7.54 (m,
11H, HPh), 7.37–7.38 (m, 6H, HPh), 7.14–7.15 (m, 4H, Himi). 31P NMR
(162 MHz, ı, ppm, CD3CN): ı = 5.19 (s, PPh2). 13C NMR (125 MHz,
ı, ppm, CD2Cl2): ı = 169.1 (s, Ir-CO), 141.32 (t, J = 42.5 Hz, CAr),
137.19 (s, CAr), 134.71 (t, J = 28.75 Hz, CAr), 132.47 (s, CAr), 131.53
(t, J = 6.25 Hz, CAr), 131.11 (d, J = 40 Hz, CAr), 128.95 (s, CAr), 128.66
(t, J = 6.25 Hz, CAr), 127.92 (t, J = 6.25 Hz, CAr), 127.55 (s, CAr), 126.24
(s, CAr). CHN-elemental analysis (found): C 53.35, H 3.52, N 6.26
(calcd., C 53.27, H 3.38, N 6.72).
Ir-complex upon coordination of L2 to Ir(acac)(CO)2 (Ir-L2a)
Under nitrogen atmosphere, a solution of L2 (90.7 mg, 0.1 mmol)
in dry CH2Cl2 (6 mL) was added to a solution of Ir(acac)(CO)2
(41.7 mg, 0.12 mmol) in CH2Cl2 (4 mL) at 40 ◦C and the resultant
mixture with presence of trace water was stirred vigorously for
ca 2 h. Then diethyl ether was added to the reaction solution to
precipitate the yellow solids, which were collected after dryness
under vacuum with the yield of 65% (74 mg). The sample suitable
for X-ray diffraction analysis was obtained by recrystallization from
CH2Cl2/diethyl ether. Due to the paramagnetic nature for the Ir(II)-
CAr), 136.27 (s, CAr), 135.39 (s, CAr), 134.06 (d, J = 26.25 Hz, CAr),
133.72 (t, J = 7.5 Hz), 130.66 (t, J = 6.25 Hz), 130.32 (quintet, J = 5 Hz,
CF3SO3), 130.11 (s, CAr), 128.93 (s, CAr), 126.84 (t, J = 30 Hz, CAr),
126.37 (s, CAr), 123.31 (t, J = 27.5 Hz, CAr), 40.36 (s, NCH3). CHN-
elemental analysis (found): C 42.48, H 3.11, N 4.82 (calcd., C 42.36,
H 2.93, N 4.82).
2.3. X-ray crystallography
Intensity data for Ir-L1a, Ir-L1b, Ir-L2a and Ir-L2b were col-
lected on a Bruker SMARTAPEX II diffractometer using graphite
monochromated Mo-K˛ radiation (ꢄ = 0.71073 Å). Data reduction
included absorption corrections by the multi-scan method. The
structures were solved by direct methods and refined by full matrix
least-squares using SHELXS-97 (Sheldrick, 1990), with all non-
hydrogen atoms refined anisotropically. Hydrogen atoms were
added at their geometrically ideal positions and refined isotropi-
cally. The crystal data and refinement details are given in Table 1.
2.4. General procedures for hydroformylation of 1-octene
In a typical experiment, Ir-L1a (0.02 mmol, or the other Ir-
complex), the ligand at the required amount, the solvent (2 mL)