M. Li, Y.-P. Hsu, Y.-H. Liu et al.
Journal of Organometallic Chemistry 927 (2020) 121537
4
.3.2. Complex 2
mined either by a Siemens SMART CCD diffractometer. The struc-
ture was solved using the SHELXS-97 program [18] and refined us-
ing the SHELXL-97 program [19] by full-matrix least-squares on F2
values.
Dark grey solid (43.1 mg, 91%): 1H NMR (400 MHz, CDCl ) δ
3
9
.01 (dd, J = 4.2, 2.0 Hz, 1H), 8.50 (d, J = 8.3 Hz, 1H), 8.30 (d,
J = 8.3 Hz, 1H), 8.22 (dd, J = 8.2, 2.0 Hz 1H), 7.56 (dd, J = 8.2,
4
2
.2 Hz, 1H), 5.90 (br, 1H), 5.18−5.08 (m, 2H), 4.05−3.95 (m, 2H),
13
4.4.1. Crystal data of complex 1
.38−2.15 (m, 4H), 1.87−1.59 (m, 4H); C NMR (100 MHz, CDCl )
3
C17 H17 IrN O , Orthorhombic; Pbcm;
a
=
10.3613(3),
δ 177.1 (C), 161.0 (C), 154.4 (C), 154.4 (CH), 142.3 (CH), 137.3 (CH),
2
2
˚
b = 13.6060(4), c = 9.9774(3) A; α = 90°, β = 90°, γ = 90°;
calcd.
1
25.3 (C), 123.6 (CH), 123.0 (CH), 65.5 (CH × 2), 64.5 (CH × 2),
3
–3
−
1
V = 1406.57(7) A˚ ; Z = 4; ρ
= 2.236 mgm ; F(000) 904;
3
2.6 (CH2 × 2), 31.2 (CH × 2); IR (KBr) 3256, 1645 cm ; ESI-
2
3
Crystal size 0.20 × 0.15 × 0.10 mm , reflections collected: 5902;
independent reflections: 1672 [R(int) = 0.0445]; θ range 2.994
to 27.489°; goodness-of-fit on F2 1.015; final R indices[I>2σ(I)]:
R1 = 0.0287, wR2 = 0.0645; R indices (all data): R1 = 0.0347,
wR2 = 0.0684. CCDC-1993080.
HRMS m/z: 472.1027 [M−H], calcd. for C
H IrN O: 472.0996.
17 3
1
7
4
.3.3. Complex 3
Brown-red solid (50.8 mg, 90%): 1H NMR (400 MHz, CDCl ) δ
.97 (dd, J = 4.2, 2.0 Hz, 1H), 8.47 (d, J = 8.4 Hz, 1H), 8.45 (ddd,
3
8
J = 4.9, 1.8, 0.9 Hz, 1H), 8.35 (d, J = 8.4 Hz 1H), 8.20 (dd, J = 8.2,
4
.4.2. Crystal data of complex 2
2
1
.0 Hz, 1H), 7.55−7.48 (m, 2H), 7.43−7.38 (m, 1H), 7.04−6.99 (m,
H), 5.30−5.00 (m, 2H), 4.66 (s, 2H), 4.25−3.95 (m, 2H), 2.30−2.05
C17 H18 IrN O; Triclinic; P-1; a = 6.9297(2), b = 10.6768(2),
3
˚
13
c = 19.8067(5) A; α = 87.914(2)°, β = 80.683(2)°, γ = 83.137(2)°;
calcd.
(
(
(
(
(
m, 4H), 1.85−1.45 (m, 4H); C NMR (100 MHz, CDCl ) δ 176.7
3
˚
3
–3
V = 1435.53(6) A ; Z = 4; ρ
= 2.186 mgm ; F(000) 904;
C), 160.9 (C), 160.9 (C), 154.3 (C), 153.9 (CH), 148.7 (CH), 142.1
CH), 137.5 (CH), 136.4 (CH), 125.2 (C), 123.5 (CH), 123.3 (CH), 121.1
3
Crystal size 0.25 × 0.20 × 0.15 mm , reflections collected: 14408;
independent reflections: 6322 [R(int) = 0.0293]; θ range 2.811
to 27.500°; goodness-of-fit on F2 0.983; final R indices[I>2σ(I)]:
R1 = 0.0257, wR2 = 0.0419; R indices (all data): R1 = 0.0336,
wR2 = 0.0455. CCDC-1993078.
CH), 120.8 (CH), 66.6 (CH × 2), 65.1 (CH × 2), 49.2 (CH ), 31.9
2
−
1
CH × 2), 31.1 (CH × 2); IR (KBr) 1632, 1619, 1607 cm ; ESI-
2
2
HRMS m/z: 563.1422 [M−H], calcd. for C
H IrN O: 563.1418.
22 4
2
3
4
.3.4. Complex 4
A mixture of L1 (17.4 mg, 0.1 mmol) and [(COD)IrCl]2 (36.9 mg,
4
.4.3. Crystal data of complex 3
C23H23IrN O; Triclinic; P-1; a = 7.4994(2), b = 9.4208(3),
4
0
.055 mmol) in a reaction tube was degassed and flushed with
˚
c = 14.2062(5) A; α = 105.687(3)°, β = 98.525(3)°, γ = 91.143(2)°;
calcd.
nitrogen. A mixture of MeOH and CH Cl (0.6: 0.6 mL) was sy-
2
2
3
–3
˚
V = 953.71(5) A ; Z = 2; ρ
= 1.963 mgm ; F(000) 548;
ringed into the tube. The resulting mixture was stirred at room
temperature for 0.5 h. All solvent were removed under vaccum.
The residue was washed with ether (2 mL x 3) to give 4 as
3
Crystal size 0.20 × 0.15 × 0.10 mm , reflections collected: 14267;
independent reflections: 8311 [R(int) = 0.03083]; θ range 2.920
to 27.496°; goodness-of-fit on F2 0.967; final R indices[I>2σ(I)]:
R1 = 0.0246, wR2 = 0.0462; R indices (all data): R1 = 0.0280,
wR2 = 0.0480. CCDC-1993077.
yellow solid (43.2 mg, 85%): 1H NMR (400 MHz, CDCl ) δ 9.28
3
(
dd, J = 4.2, 1.9 Hz, 1H), 8.46 (d, J = 8.2 Hz, 1H), 8.38 (dd,
J = 8.1, 1.9 Hz, 1H), 8.30 (d, J = 8.2 Hz 1H), 7.71 (dd, J = 8.1,
.2 Hz, 1H), 5.03−4.94 (m, 2H), 4.75−4.70 (m, 1H), 3.69−3.64
4
4
.4.4. Crystal data of complex 4
(
m, 1H), 3.02−2.92 (m, 1H), 2.82−2.72 (m, 1H), 2.70−2.61 (m,
C17 H18 ClIrO N2 (CH Cl )0.5; Triclinic; P-1;
a
=
7.9006(3),
2
2
2
1
2
H), 2.59−250 (m, 1H), 2.46−2.37 (m, 1H), 2.16−2.08 (m, 1H),
13
˚
b = 14.1525(5), c = 16.8773(6) A; α = 109.292(3)°, β = 90.187(3)°,
calcd.
.04−1.96 (m, 1H), 1.73−1.64 (m, 1H), -11.54 (s, 1H); C NMR
3
–3
˚
γ = 104.804(3)°; V = 1714.05(11) A ; Z = 4; ρ
= 2.141 mgm
;
(
100 MHz, CDCl ) δ 172.5 (C), 156.2 (C), 155.5 (CH), 150.1 (C), 141.9
3
3
F(000) 1060; Crystal size 0.30 × 0.25 × 0.20 mm , reflections col-
lected: 16453; independent reflections: 7649 [R(int) = 0.0386];
θ range 2.858 to 27.500°; goodness-of-fit on F2 1.065; final R
indices[I>2σ(I)]: R1 = 0.0349, wR2 = 0.0842; R indices (all data):
R1 = 0.0404, wR2 = 0.0885. CCDC-1993079.
(
CH), 138.4 (CH), 125.6 (C), 125.5 (CH), 125.0 (CH), 82.1 (CH), 81.5
(
CH × 2), 80.3 (CH), 35.5 (CH ), 31.5 (CH ), 29.2 (CH ), 28.1 (CH );
2
2
2
2
−1
IR (KBr) 2267, 1666 cm
.
4
.3.5. Complex 5
A mixture of L1 (17.4 mg, 0.1 mmol), [(COD)IrCl]2 (33.6 mg,
4.4.5. Crystal data of complex 5
0
.05 mmol), and 0.2 M HCl methanol solution (0.3 mL) in CH Cl2
2
C17 H17 Cl IrN O (CH Cl ); Triclinic; P-1;
a
=
11.3387(7),
2
2
2
2
2
(
0.3 mL) was placed in a reaction tube. The mixture was stirred at
˚
b = 11.9004(4), c = 16.8421(10) A; α = 84.943(4)°, β = 73.409(5)°,
calcd.
room temperature for 1.5 in the presence of air. Water (1 mL) was
added the reaction mixture. Extraction of mixture with CH Cl (3
˚ 3
–3
γ = 67.528(4)°; V = 2012.0(2) A ; Z = 4; ρ
= 2.078 mgm
;
3
2
2
F(000) 1208; Crystal size 0.25 × 0.25 × 0.20 mm , reflections
collected: 16795; independent reflections: 7078 [R(int) = 0.0255];
θ range 2.919 to 25.000°; goodness-of-fit on F2 1.035; final R
indices[I>2σ(I)]: R1 = 0.02171, wR2 = 0.0483; R indices (all data):
R1 = 0.0254, wR2 = 0.0502. CCDC-1993076.
mL x 3) and the combined extracts were dried and concentrated.
The residue was chromatographed on silica gel with elution of 1%
MeOH in CH Cl2 to give 5 as light yellow solid (48.1 mg, 88%): 1
H
2
NMR (400 MHz, DMSO-d ) δ 9.20 (dd, J = 4.2, 1.9 Hz, 1H), 9.03 (d,
6
J = 8.3 Hz, 1H), 8.77 (dd, J = 8.2, 1.9 Hz, 1H), 8.29 (d, J = 8.3 Hz,
1
H), 7.96 (dd, J = 8.2, 4.2 Hz, 1H), 6.95−6.89 (m, 2H), 5.95−5.89
4.5. Catalysis
13
(
m, 2H), 2.76−2.63 (m, 4H), 2.39−2.15 (m, 4H); C NMR (100 MHz,
DMSO-d ) δ 174.4 (C), 157.0 (CH), 154.5 (C), 150.9 (C), 144.8 (CH),
Typical procedure for the amination is following: a mixture of
6
1
39.2 (CH), 126.0 (C), 125.5 (CH), 124.4 (CH), 99.0 (CH × 2), 96.7
amine (1 mmol), alcohol (5 mmol), Cs CO3 (0.5 mmol) and Ir com-
2
−1
−3
(
CH × 2), 31.3 (CH × 2), 28.2 (CH × 2); IR (KBr) 1684 cm ; ESI-
plex (5 × 10 mmol) was heated at 120 °C under nitrogen atmo-
2
2
+
HRMS m/z: 545.0343 [M+H], calcd. for C
H
N O Cl Ir [M + H]
sphere for 20 h. After the completion, water (3 mL) was added.
17
18
2
2
2
5
45.0375.
The mixture was extracted with CH Cl2 (5 mL x 3). All organic ex-
2
tracts were combined and dried over magnesium sulfate, and then
concentrated. Products were purified by chromatography with elu-
tion of hexane/EtOAc and characterized by 1H and 13C NMR spec-
troscopy. All products are known compounds and their spectro-
scopic data are consistent with literature.
4
.4. X-ray crystallographic analysis
Crystals suitable for X-ray determination were obtained by re-
crystallization at room temperature. Cell parameters were deter-
6