Inorganic Chemistry
Article
.21 (d, J3 = 7.8 Hz, 1H, H ), 7.17 (dd, J
3
= 5.0 Hz, J4 = 1.6
127.0, 124.8, 123.8, 120.8, 119.7, 115.9, 106.2, 100.3, 93.0, 28.3, 18.4,
7
HH
g
HH
HH
+
Hz, 1H, H ), 2.30 (s, 3H, H ), 1.16 (pseudosinglet, 21H, H + H ).
C{ H} NMR (176 MHz, CDCl ): δ 157.2, 149.9, 149.5, 139.3,
39.2, 135.1, 134.0, 129.7, 129.1, 129.0, 128.7, 126.9, 123.6, 122.4,
20.9, 106.6, 91.3, 20.1, 18.6, 11.3. ES-MS: m/z 426.243 ([M + H] ).
11.3. MS-MALDI: 1112.4 ([M] ). Anal. Calcd for C H N IrO Si :
b
j
k
i
61 71
2
2
2
13
1
C, 65.85; H, 6.43; N, 2.52. Found: C, 65.81; H, 6.60; N, 2.42.
3
C
4
1
1
Ir(L )
(acac) (4). 4 was a bright-green powder. Crystals were grown
2
1
+
by slow evaporation of a benzene solution. Yield: 714 mg (57%). H
NMR (CD
7.60 (dd, J HH = 7.8 Hz, J HH = 1.3 Hz, 2H, H
7.48 (dd, J HH = 7.7 Hz, J HH = 1.7 Hz, 2H, H
3
Anal. Calcd for C H NSi: C, 81.82; H, 8.29; N, 3.29. Found: C,
2
Cl
2
): δ 8.55 (d, J HH = 5.7 Hz, 2H, H
a
), 7.84 (s, 2H, H
c
),
),
29
35
3
4
8
1.90; H, 8.35; N, 3.46.
-Phenyl-4-[2,3,5,6-tetramethyl-4-[(triisopropylsilyl)ethynyl]-
phenyl]pyridine (L H). The same procedure as that for L H, except 4-
2,3,5,6-tetramethyl-4-[(triisopropylsilyl)ethynyl]phenyl]pyridine in
g
), 7.52 (s, 2H, H
), 7.39 (d, J HH = 7.8
= 1.9 Hz, 2H, H ), 6.87
k
3
4
3
2
i
5
1
3
3
Hz, 2H, H ), 7.19 (dd, J
= 5.9 Hz, J
j
HH HH
b
3
4
HH
3
HH
[
(td, J
HH
= 7.4 Hz, J
= 1.3 Hz, 2H, H ), 6.75 (td, J
= 7.4 Hz,
HH
f
4
3
4
place of 4-(2,3,5,6-tetramethylphenyl)pyridine, was used to give a
J
= 1.4 Hz, 2H, H ), 6.37 (dd, J
= 7.7 Hz, J
= 1.2 Hz, 2H,
e
HH
HH
1
yellow oil. Yield: 4.50 g (41%). H NMR (700 MHz, CDCl ): δ 8.75
H ), 5.35 (s, 1H, H ), 2.44 (s, 6H, H ), 1.86 (s, 6H, H ), 1.18
3
H
d o h n
d, J3 = 4.9 Hz, J4 = 0.9 Hz, 1H, H ), 8.02 (dd, J
3
= 7.0 Hz,
(pseudosinglet, 42 H, H + H ). C{ H} NMR (176 MHz, CD Cl ):
l m 2 2
13
1
(
HH
HH
a
HH
4
J
= 1.2 Hz, 2H, H ), 7.50 (s, 1H, H ), 7.49−7.46 (m, 2H, H ),
δC 184.7, 167.9, 150.2, 147.6, 147.5, 145.0, 138.7, 135.6, 134.1, 133.1,
HH
d
c
e
3
4
HH
7
.43−7.40 (m, 1H, H ), 7.00 (dd J
= 4.9 Hz, J = 1.5 Hz, 1H,
129.6, 129.3, 128.8, 128.2, 123.8, 122.4, 120.8, 118.9, 106.5, 100.4,
f
HH
+
H ), 2.49 (s, 6H, H ), 1.93 (s, 6H, H ), 1.16 (pseudosinglet, 21H, H
91.6, 28.3, 20.0, 18.4, 11.3. MS-MALDI: 1140.5 ([M] ). Anal. Calcd
b
g
h
i
+
Hj). 13C{ H} NMR (176 MHz, CDCl ): δ 157.5, 151.5, 149.7,
1
for C H N IrO Si : C, 66.34; H, 6.63; N, 2.46. Found: C, 66.47; H,
3
C
63 75
2
2
2
1
1
39.5, 139.0, 136.6, 130.9, 129.1, 128.7, 126.9, 123.8, 123.0, 121.2,
6.75; N, 2.59.
5
05.3, 99.0, 18.7, 18.5, 17.8, 11.3. MS-ASAP: m/z 468.308 ([M +
Ir(L ) (acac) (5). 5 was a bright-green powder. Yield: 552 mg
2
+
1
3
H] ). Anal. Calcd for C H NSi: C, 82.17; H, 8.84; N, 2.99. Found:
C, 81.99; H, 8.93; N, 3.22.
Iridium Coordination General Procedure. IrCl ·3H O (408 mg,
(41%). H NMR (700 MHz, CD Cl ): δ 8.58 (d, J
= 6.0 Hz, 2H,
3
2
41
2
2
H
HH
3
4
H ), 7.66 (s, 2H, H ), 7.54 (dd, J
= 7.8 Hz, J
= 1.4 Hz, 2H,
a
c
HH
HH
3
HH
4
3
H ), 7.00 (dd, J
= 5.7 Hz, J
= 1.8 Hz, 2H, H ), 6.86 (td, J
= 7.4 Hz, J
= 1.2 Hz, 2H, H ), 5.37 (s, 1H,
HH d
=
HH
3
2
g
HH
b
1
5
4
3
4
HH
1
.1 mmol) was added to a solution containing L H−L H (3.48
7.4 Hz, J
= 1.3 Hz, 2H, H ), 6.76 (td, J
= 1.3 Hz,
HH
f
HH
3
4
mmol), ethoxyethanol (30 mL), and water (15 mL). The solution was
2H, H ), 6.39 (dd, J
= 7.7 Hz, J
e
HH
heated to 110 °C for 12 h before being cooled and poured into water
H ), 2.55−2.54 (m, 12H, H + H ), 2.11 (s, 6H, H or H ), 2.04 (s,
o
h
i
j
k
(
300 mL), forming a precipitate. The precipitate was dissolved in
6H, H or H ), 1.87 (s, 6H, H ), 1.20 (pseudosinglet, 42H, H + H ).
j k n l m
1
3
1
DCM and dried over MgSO before being passed through a silica
C{ H} NMR (176 MHz, CD Cl ): δ 184.7, 168.2, 152.0, 148.0,
2 2 C
4
plug. The residue was dissolved in ethoxyethanol (30 mL),
acetylacetone (5 mL) and K CO (276 mg, 2.0 mmol) were added,
and the solution was heated to 90 °C for 12 h. The solution was
cooled and poured into water (300 mL), forming a precipitate, which
was collected via filtration. The precipitate was dissolved in DCM and
dried over MgSO4 before the product was purified via silica
147.4, 145.2, 139.0, 136.6, 133.0, 131.1, 128.8, 123.9, 123.7, 123.0,
120.7, 119.6, 105.4, 100.4, 99.0, 28.3, 18.5, 18.3, 17.7, 11.4. MS-
2
3
+
MALDI: m/z 1224.5 ([M] ). Anal. Calcd for C H N O Si Ir: C,
6
9
87
2
2
2
67.66; H, 7.16; N, 2.29. Found: C, 67.49; H, 6.93; N, 2.36.
Sonogashira Coupling General Procedure. THF (50 mL) and
Et N (5 mL) were added to triisopropylsilyl (TIPS)-protected
3
chromatography eluted by DCM, collecting the emissive band.
complexes 2−5 (0.20 mmol), 4-tert-butyliodobenzene or 1-tert-
1
Ir(L ) (acac) (1). 1 was a bright-green solid. Crystals were grown by
butyl-4-(4-iodophenyl)ethynylbenzene (0.50 mmol), Pd(PPh ) (46
2
3 4
1
evaporation of a DCM/hexane solution. Yield: 589 mg (62%). H
mg, 0.04 mmol), and CuI (8 mg, 0.04 mmol). The solution was
degassed by three freeze−pump−thaw cycles before tetrabutylammo-
nium fluoride (TBAF; 1.0 M in THF, 0.50 mL, 0.50 mmol) was
added. The solution was stirred at room temperature for 12 h before
the solvent was removed. The residue was purified by silica
chromatography eluted by DCM, collecting the emissive band.
3
NMR (700 MHz, CD Cl ): δ 8.59 (dd J
= 5.7 Hz, 2H, H ), 7.69
2
2
H
HH
a
3
4
(
2
d, J4 = 2.0 Hz, 2H, H ), 7.55 (dd, J
= 7.8 Hz, J
= 1.7 Hz,
HH
HH
c
HH
3
4
H, H ), 7.09 (s, 2H, H ), 7.03 (dd, J
= 5.8 Hz, J
= 1.7 Hz, 2H, H ), 6.76 (td, J
= 1.7 Hz, 2H, H ), 6.41 (dd, J
= 1.8 Hz, 2H,
g
h
HH
HH
3
HH
4
3
H ), 6.86 (td, J
7
= 7.4 Hz, J
=
HH
b
HH
f
4
3
4
.4 Hz, J
= 7.8 Hz, J
= 1.6
HH
e
HH
HH
6
1
Hz, 2H, H ), 5.38 (s, 1H, H ), 2.33−2.32 (m, 12H, H + H ), 2.09 (s,
Ir(L ) (acac) (6). 6 was an orange solid. Yield: 158 mg (87%). H
2
3
d
m
i
j
1
3
1
6
H, H or H ), 2.02 (s, 6H, H or H ), 1.88 (s, 6H, H ). C{ H}
NMR (700 MHz, CDCl ): δ 8.46 (d, J
(s, 2H, Hc), 7.57−7.53 (m, 6H, H + H ), 7.44 (d, J
H ), 7.18 (dd, J
= 5.9 Hz, 2H, H ), 7.92
HH a
l
k
l
k
n
3
H
3
NMR (176 MHz, CD Cl ): δ 184.7, 168.1, 152.3, 147.9, 147.4,
= 8.0 Hz, 4H,
2
2
C
g
h
HH
3
4
3
1
1
45.3, 138.9, 133.9, 133.0, 131.2, 131.1, 128.7, 123.8, 123.2, 120.7,
19.8, 100.4, 28.3, 19.8, 16.9. MS-MALDI: m/z 864.4 ([M] ). Anal.
= 5.9 Hz, J
= 1.9 Hz, 2H, H ), 6.82 (td, J
=
HH
= 1.3 Hz,
i
HH
HH
b
+
4
HH
3
4
7.8 Hz, J
= 1.2 Hz, 2H, H ), 6.72 (td, J
= 7.7 Hz, J
HH d
f
HH
HH
3
4
Calcd for C H N O Ir: C, 65.33; H, 5.48; N, 3.24. Found: C, 65.29;
2H, H ), 6.31 (dd, J
= 7.7 Hz, J
= 1.2 Hz, 2H, H ), 5.21 (s, 1H,
47
47
2
2
e
HH
1
3
1
H, 5.33; N, 3.38.
H ), 1.79 (s, 6H, H ), 1.35 (s, 18H, H ). C{ H} NMR (176 MHz,
k l j
2
Ir(L ) (acac) (2). 2 was a bright-orange powder. Crystals were
CD Cl ): δ 184.8, 167.9, 153.1, 147.7, 147.4, 144.4, 136.9, 133.1,
2 2 C
2
grown by evaporation of an acetonitrile solution. Yield: 0.57 g (60%).
132.5, 131.7, 129.0, 127.5, 125.6, 123.9, 123.5, 120.9, 120.3, 118.7,
1
3
+
H NMR (700 MHz, CD Cl ): δ 8.43 (d, J
= 6.0 Hz, 2H, H ),
100.3, 96.1, 85.8, 34.8, 30.8, 28.2. MS-MALDI: m/z 912.4 ([M] ).
2
2
H
HH
A
.90 (d, J4 = 1.7 Hz, 2H), 7.59 (dd, J
3
= 7.7 Hz, J
= 1.7 Hz, 2H, H ), 6.87 (td,
4
= 1.1 Hz,
Anal. Calcd for C H N IrO · / CH Cl : C, 63.69; H, 5.01; N, 2.87.
3
7
2
J
HH
HH
HH
51 47
2
2
4
2
2
3
4
H, H ), 7.20 (dd, J
= 7.7 Hz, J
.1 Hz, 2H, H ), 6.27 (dd, J
= 6.0 Hz, J
Found: C, 63.40; H, 5.38; N, 2.89.
Ir(L ) (acac) (7). 7 was a red powder. Crystals were grown by
evaporation of a DCM/hexane solution. Yield: 200 mg (90%). H
NMR (700 MHz, CDCl ): δ 8.48 (d, J
G
HH
HH
B
3
4
3
4
7
= 1.1 Hz, 2H, H ), 6.71 (td, J
= 7.7 Hz, J
=
HH
HH
F
HH
HH
2
3
4
1
1
5
= 7.7 Hz, J
= 1.1 Hz, 2H, H ),
E
HH
HH
D
1
3
1
3
.28 (s, 1H, H ), 1.80 (s, 6H, H ), 1.20 (m, 42 H, HH+I). C{ H}
= 5.9 Hz, 2H, H ), 7.93
HH a
J
K
3
H
4
NMR (176 MHz, CD Cl ): δ 184.9, 168.5, 147.8, 144.1, 133.3,
(d, J
= 1.8 Hz, 2H, H ), 7.59−7.55 (m, 10H, H + H + H ), 7.48
= 8.2 Hz, 4H, H ), 7.39 (d, J
2
2
C
HH
c
g
i
k
3
3
1
1
6
32.3, 129.5, 124.2, 124.0, 121.1, 120.8, 104.0, 101.0, 98.9, 28.9, 18.8,
(d, J
= 8.2 Hz, 2H, H ), 7.19 (dd,
HH
j
HH k
+
3
HH
4
3
HH
4
1.4. MS-MALDI: 960.2 ([M] ). Anal. Calcd for C H N IrO Si : C,
J
= 5.8, J
Hz, 2H, H ), 6.72 (td, J
(dd, J
= 1.8 Hz, 2H, H ), 6.82 (td, J
= 7.4 Hz, J
= 1.2 Hz, 2H, H ), 6.30
HH e
= 1.2
HH
4
9
63
2
2
2
HH
b
3
4
1.28; H, 6.61; N, 2.92. Found: C, 61.33; H, 6.70; N, 3.04.
= 7.4 Hz, J
f
HH
3
3
4
Ir(L ) (acac) (3). 3 was a bright-orange powder. Crystals were
= 7.8 Hz, J
= 1.1 Hz, 2H, H ), 5.22 (s, 1H, H ), 1.80 (s,
2
HH
HH d m
1
13
1
grown by evaporation of a DCM solution. Yield: 831 mg (68%). H
NMR (700 MHz, CD Cl ): δ 8.60 (d, J
6H, H ), 1.33 (s, 18H, H ). C{ H} NMR (176 MHz, CDCl ): δ
n
l
3
C
3
= 6.0 Hz, 2H, H ), 8.12
184.7, 168.5, 151.9, 147.7, 143.9, 133.0, 131.9, 131.6, 131.4, 129.4,
125.4, 124.6, 123.2, 121.3, 120.9, 120.3, 119.7, 100.4, 95. MS-
2
2
H
HH
a
3
3
(
s, 2H, H ), 7.81 (d, J
= 8.0 Hz, 4H, H ), 7.71 (d, J
= 7.9 Hz,
c
HH
j
HH
4
3
+
J
J
= 1.3 Hz, 2H, H ), 7.68 (d, J
= 8.0 Hz, 4H, H ), 7.43 (dd,
M A L D I : m / z 1 1 1 2 . 3 ( [ M ] ) . A n a l . C a l c d f o r
HH
g
HH
i
3
= 6.0 Hz, J4 = 2.1 Hz, 2H, H ), 6.90 (td, J
3
HH
4
11
= 7.4 Hz, J
=
C H N IrO · / CH Cl : C, 67.27; H, 4.76; N, 2.30. Found: C,
HH
HH
b
HH
67 55
2
2
4
2
2
3
4
1
(
.2 Hz, 2H, H ), 6.74 (td, J
= 7.4 Hz, J
= 1.3 Hz, 2H, H ), 6.37
67.06, H; 4.67; N, 2.31.
f
HH
HH
e
dd, J3 = 6.0 Hz, J
4
= 1.2 Hz, 2H, H ), 5.32 (s, 1H), 1.85 (s, 6H),
Ir(L ) (acac) (8). 8 was an orange powder. Yield: 189 mg (89%). H
2
3
8
1
HH
HH
d
1
3
1
1
1
.19 (pseudosinglet, 42 H). C{ H} NMR (176 MHz, CD Cl ): δ
84.8, 168.3, 148.4, 148.2, 147.5, 144.9, 137.1, 133.2, 132.6, 128.9,
NMR (700 MHz, CD Cl ): δ 8.57 (d, J
= 6.0 Hz, 2H, H ), 8.13
HH a
2
2
C
2
2
H
4
3
HH
(d J
= 2.0 Hz, 2H, H ), 7.85 (d, J
= 8.0 Hz, 4H, H ), 7.74 (d,
HH
c
h
C
Inorg. Chem. XXXX, XXX, XXX−XXX