Organometallics
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solution was stirred overnight at room temperature to give a dark red
solution. The solvent was removed under vacuum to give the
compound as a red solid. Yield: 98% (0.480 g). Anal. Calcd for
C H IrNO : C, 44.07; H, 4.11; N, 2.86. Found: C, 44.19; H, 4.34; N,
mmol) was dissolved in CH Cl (20 mL) to give an orange solution,
2
2
which was stirred at room temperature for 48 h. The solution was
concentrated under reduced pressure to ca. 3 mL and then
chromatographed on a silica gel column using CH Cl as eluent.
18
20
3
2
2
1
2
8
.82. H NMR (400.162 MHz, 298 K, THF-d ): δ 8.18 (d, 1H, J
.8 Hz, H-4), 7.65 (d, 1H, JH−H = 8.0 Hz, H-3), 7.31 (t, 1H, JH−H = 8.0
=
Concentration of the obtained solution under vacuum and addition of
pentane gave the compound as an orange solid, which was filtered,
washed with pentane, and dried under vacuum. Yield: 62% (0.085 g).
Anal. Calcd for C H BrIrN O : C, 42.59; H, 3.73; N, 4.32. Found: C,
8
H−H
Hz, H-6), 6.84 (d, 1H, JH−H = 8.0 Hz, H-5), 6.71 (d, 1H, JH−H = 8.0
Hz, H-7) (hqca), 5.11 (br, 2H, CH, coe), 2.20 (m, 2H), 2.02 (m,
2
3
24
2
3
+
2
H), 1.74 (m, 4H), 1.46−1.40 (m, 4H) (>CH coe), −36.26 (s, 1H,
42.61; H, 3.56; N, 4.27. MS (MALDI, CH Cl , m/z): 649.1 [M + H] ,
2,
2 2
13
1
+
+
+ 1
Ir−H) (n = 1). C{ H} NMR (75.468 MHz, 298 K, THF-d ): δ
539.0 [M − coe] , 491.1 [M − Br − py] , 459.1 [M − coe − py] . H
NMR (400.162 MHz, 298 K, CD Cl ): δ 8.46 (dd, 2H, J = 8.8, 1.4
8
1
3
2
42.21 (C-9), 134.69 (C-6), 130.94 (C-4), 130.04 (C-10), 118.92 (C-
2
2
H−H
), 112.48 (C-7), 110.46 (C-5) (hqca), 80.91, 80.69 (CH, coe),
Hz, o-H, py), 8.04 (d, 1H, JH−H = 8.8 Hz, H-4), 7.72 (d, 1H, JH−H = 8.8
Hz, H-3) (hqca), 7.66 (m, 1H, JH−H = 7.3 Hz, p-H, py), 7.47 (t, 1H,
JH−H = 8.0 Hz, H-6, hqca), 7.26 (t, 2H, JH−H = 7.3 Hz, m-H, py), 7.05
(d, 1H, JH−H = 8.0 Hz, H-5), 6.96 (d, 1H, JH−H = 8.0 Hz, H-7) (hqca),
6.06 (m, 2H, CH, coe), 2.04 (m, 2H), 1.84 (m, 2H), 1.64−1.50 (set
9.66, 29.54, 26.42, 26.36, 24.70, 24.67 (>CH , coe) (n = 1). MS
2
+
−1
(
MALDI, THF, m/z): 489.1 [M − H] . IR (THF, cm ): ν(Ir−H)
1
2269 (s); ν(CO) 1683 (s). H NMR (400.162 MHz, 298 K, C D ): δ
6 6
7.17 (d, JH−H = 8.8 Hz), 7.09 (d, JH−H = 8.4 Hz), 7.01 (d, JH−H = 8.8
13
1
Hz), 6.89 (t, JH−H = 7.3 Hz) (hqca), 6.84−6.75 (m, hqca and 1H
of m, 6H), 1.28 (m, 2H) (>CH , coe). C{ H} NMR (75.468 MHz,
2
CH, coe), 6.75−6.68 (m), 6.63 (d, J = 7.3 Hz), 6.57 (d, J = 8.8
298 K, CD Cl ): δ 148.77 (2C, py), 143.81 (C-9, hqca), 139.30 (py),
H−H
H−H
2
2
Hz), 6.38 (d, J
= 8.8 Hz) (hqca), 6.31 (br, 1H, CH, coe), 6.28
137.52 (C-6), 133.36 (C-4), 131.82 (C-10) (hqca), 125.69 (2C, py),
H−H
(
d, JH−H = 8.4 Hz), 6.18 (t, J
= 8.4 Hz), 6.12 (d, J
= 7.3 Hz),
H−H
121.52 (C-3), 116.15 (C-7), 114.00 (C-5) (hqca), 92.76, 92.44 (
H−H
6
5
1
.04 (dd, JH−H = 7.0, 2.2 Hz) (hqca), 5.74 (m, 1H, JH−H = 4.0 Hz),
.66 (m, 3H, JH−H = 4.4 Hz), 5.45 (m, 1H, JH−H = 4.0 Hz), 4.21 (br,
CH, cod), 30.08, 29.96, 26.39, 26.35, 26.18, 26.12 (>CH , coe). IR
2
−1
(ATR, cm ): ν(CO) 1674 (s).
3
H) (CH, coe), 2.60−0.50 (set of m, >CH , coe), −33.54 (s),
[IrH(κ -hqca)(py) ] (6). A resealable Schlenk tube equipped with a
2
3
2
−
34.03 (s), −34.38 (s) −35.98 (s) (Ir−H) (n = 2). MS (ESI, toluene,
Teflon screw valve was charged with [IrH(κ -hqca)(coe)] (3; 0.490 g,
1.00 mmol), pyridine (3 mL), and THF (50 mL). The mixture was
heated at 75 °C for 12 h to give a dark red solution. After removal of
volatiles, the resulting red solid was dissolved in the minimum amount
+
+
−1
m/z): 1003.2 (M + Na ), 981.2 (M + H ). IR (ATR, cm ): ν(Ir−H)
2255 (s); ν(CO) 1615 (s).
3
[
IrD(κ -hqca)(coe)] (3-d ). MeOH-d (15 μL) was added to a NMR
1 4
3
tube containing a solution of [IrH(κ -hqca)(coe)] (3; 10 mg) in THF
of CH Cl (6 mL). Then, n-pentane (25 mL) was slowly added and
2 2
2
(
0.6 mL). D NMR (61.422 MHz, 298 K, THF): δ −34.72 (s, Ir−D).
the resulting mixture kept at low temperature to afford a red solid,
which was filtered, washed with n-pentane, and dried in vacuo. Yield:
3
[
IrH(κ -hqca)(coe)(CH CN)] (3·CH CN). Acetonitrile (6 μL) was
3
3
3
added to a solution of [IrH(κ -hqca)(coe)] (3) in toluene-d (0.5
mL). H NMR (300.125 MHz, 223 K, toluene-d ): δ 7.81 (bs, 1H),
93% (0.500 g). Anal. Calcd for C20
H
16IrN
3
O
3
: C, 44.60; H, 2.99; N,
Cl , m/z):
, m/z): 617.1 [M + py] , 461.1 [M
Cl ): δ 8.86 (dd, 2H,
H−H = 6.6, 1.4 Hz, cis-py), 8.50−8.47 (m, 2H, trans-py), 7.82 (d, 1H,
H−H = 8.8 Hz, H-4, hqca), 7.78 (tt, 1H, JH−H = 7.3, 1.4 Hz, cis-py),
8
1
7.80. Found: C, 44.79; H, 2.76; N, 7.61. MS (MALDI, CH
8
2
2
+
+
7
.33−7.08 (m, 3H), 6.68 (bs, 1H) (hqca), 5.68 (bs, 2H, CH), 2.47
617.2 [M + py] . MS (ESI, CH Cl
2 2
+
1
(
bs, 2H, >CH ) (coe), 2.25 (s, 3H, CH CN), 2.02−1.20 (m, 8H,
− py] . H NMR (400.162 MHz, 298 K, CD
2
2
2
3
>
CH , coe), −28.34 (bs, 1H, Ir−H).
J
J
2
3
3
[
IrH(κ -hqca)(coe)(CH OH)] (3·CH OH). Compound [IrH(κ -
3
3
hqca)(coe)] (3; 10 mg) was dissolved in a 1/1 THF/MeOH mixture
1 mL). The solvent was removed under vacuum and the residue
7.60 (tt, 1H, JH−H = 7.3, 1.4 Hz, trans-py), 7.47 (d, 1H, JH−H = 8.8 Hz,
H-3), 7.31 (t, 1H, JH−H = 8.0 Hz, H-6) (hqca), 7.27 (t, 2H, JH−H = 7.3
Hz, cis-py), 7.20 (t, (t, 2H, JH−H = 7.3 Hz, trans-py), 6.81 (d, 1H, JH−H
= 8.0 Hz, H-5), 6.79 (d, 1H, JH−H = 8.0 Hz, H-7) (hqca), −23.31 (s,
(
1
dissolved in C D . H NMR (400.162 MHz, C D , room temper-
6
6
6
6
ature): δ 7.70 (d, 1H, JH−H = 8.8 Hz, H-4), 7.63 (d, 1H, JH−H = 8.8 Hz,
H-3), 7.29 (t, 1H, JH−H = 8.0 Hz, H-6), 7.07 (d, 1H, JH−H = 8.0 Hz, H-
13
1
1H, Ir−H). C{ H} NMR (75.468 MHz, 298 K, CD Cl ): δ 177.04
2 2
5), 6.72 (d, 1H, JH−H = 8.0 Hz, H-7) (hqca), 5.55 (d, 2H, JH−H = 8.8
(CO), 173.33 (C-8) (hqca), 153.96, 153.91 (cis-py), 148.51, 148.41
(trans-py), 146.43 (C-2), 145.77 (C-9) (hqca), 137.68 (trans-py),
137.04 (cis-py), 134.09 (C-6, hqca), 132.36 (2C, cis-py), 131.46 (C-
10), 125.73 (C-4), (both s, hqca), 125.60 (2C, trans-py), 120.73 (C-3),
Hz, CH-, coe), 4.60 (CH OH), 3.30 (t, 3H, CH OH), 2.60−1.50
3
3
(
10H, >CH , coe), −34.24 (Ir−H).
2
3
[
IrH(κ -hqca)(coe)(py)] (4). Pyridine (2 mL) was added to a
3
−1
solution of [IrH(κ -hqca)(coe)] (3; 0.245 g, 0.500 mmol) in THF (50
mL). Stirring at room temperature for 14 h afforded an orange
solution. After removal of solvent, the resulting orange solid was
dissolved in the minimum volume of dichloromethane (10 mL).
Addition of pentane (30 mL) led to the precipitation of a red-orange
solid, which was filtered, washed with pentane (3 × 10 mL), and dried
under vacuum. Yield: 97% (0.276 g). Anal. Calcd for C H IrN O :
114.96 (C-5), 112.61 (C-7) (hqca). IR (ATR, cm ): ν(Ir−H) 2140
(s); ν(CO) 1651 (s).
[IrH(κ -hqca)(2-Mepy) ] (7). To a solution of [IrH(κ -hqca)(coe)]
3
3
2
(3; 0.245 g, 0.500 mmol) in THF (40 mL) was added 2-
methylpyridine (2 mL). Stirring at room temperature for 14 h
afforded a red solution. After removal of volatiles under reduced
pressure, the resulting red solid was dissolved in the minimum volume
of dichloromethane (10 mL). Addition of pentane (30 mL) led to the
precipitation of a red-orange solid, which was filtered, washed with
pentane (3 × 10 mL), and dried in vacuo. Yield: 94% (0.266 g). Anal.
23
25
2
3
C, 48.49; H, 4.42; N, 4.92. Found: C, 48.33; H, 4.38; N, 4.79. MS
+
(
MALDI, CH Cl , m/z): 491.2 (M - py). MS (ESI, CH CN, m/z):
2
2
3
+
+ 1
5
69.2 [M − H] , 490.1 [M − py − H] . H NMR (400.162 MHz, 298
K, CD Cl ): δ 8.44 (dm, 2H, J
= 6.6 Hz, o-H, py), 7.97 (d, 1H,
Calcd for C22
H, 3.76; N, 7.61. MS (MALDI, CH
MS (ESI, CH CN, m/z): 659.2 [M + 2-Mepy] , 475.1 [M − 2-
Mepy] . H NMR (400.162 MHz, 298 K, CD Cl ): δ 8.47 (d, 1H,
H−H = 5.8 Hz, cis-2-Mepy), 8.00 (d, 1H, JH−H = 5.1 Hz, trans-2-Mepy),
H20IrN O : C, 44.63; H, 3.56; N, 7.42. Found: C, 44.79;
3 3
2
2
H−H
+
JH−H = 8.0 Hz, H-4, hqca), 7.63 (tt, 1H, JH−H = 6.6, 1.5 Hz, p-H, py),
.58 (d, 1H, JH−H = 8.0 Hz, H-3), 7.36 (t, 1H, JH−H = 8.0 Hz, H-6)
hqca), 7.25 (t, 2H, JH−H = 5.8 Hz, m-H, py), 6.88 (d, 1H, JH−H = 8.0
Cl , m/z): 474.9 [M − 2-Mepy].
2 2
+
7
(
3
+
1
2
2
Hz, H-5), 6.84 (d, 1H, JH−H = 8.0 Hz, H-7) (hqca), 4.96 (m, 2H,
J
CH, coe), 2.25−2.09 (m, 4H,), 1.85−1.78 (m, 2H), 1.64−1.55 (m,
7.91 (d, 1H, JH−H = 8.8 Hz, H-4, hqca), 7.68 (td, 1H, JH−H = 7.3, 1.5
Hz, cis-2-Mepy), 7.53 (d, 1H, JH−H = 8.80 Hz, H-3, hqca), 7.52 (td,
1H, JH−H = 7.7, 1.5 Hz, trans-2-Mepy), 7.40 (d, 1H, JH−H = 5.1 Hz, cis-
1
3
1
2
H), 1.45−1.36 (m, 4H) (>CH , coe), −26.48 (1H, Ir−H). C{ H}
2
NMR (75.468 MHz, 298 K, CD Cl ): δ 172.08 (C-8, hqca), 148.37,
2
2
148.19 (py), 143.57 (C-2), 142.67 (C-9) (hqca), 138.37 (py), 136.21
2-Mepy), 7.37 (t, 1H, JH−H = 8.1 Hz, H-6, hqca), 7.07 (d, 1H, JH−H =
(
(
3
C-6), 133.29 (C-4), 132.29 (C-10), (hqca), 125.97 (2C, py), 121.57
8.0 Hz, trans-2-Mepy), 6.99 (t, 1H, JH−H = 6.6 Hz, cis-2-Mepy), 6.95 (t,
1H, JH−H = 6.6 Hz, trans-2-Mepy), 6.89 (d, 1H, JH−H = 8.1 Hz, H-5),
C-3), 115.13 (C-7), 113.00 (C-5) (hqca), 83.78, 83.62 (CH, coe),
−1
2.31, 32.18, 29.70, 29.60, 27.12, 27.08 (>CH , coe). IR (ATR, cm ):
6.79 (d, 1H, JH−H = 8.0 Hz, H-7) (hqca), 2.81 (s, 3H, −CH
Mepy), 2.12 (s, 3H, −CH , trans-2-Mepy), −26.06 (s, 1H, Ir−H).
C{ H} NMR (75.468 MHz, 298 K, CD Cl
3
, cis-2-
2
ν(Ir−H) 2211 (s); ν(CO) 1671 (s).
3
3
3
13
1
[
IrBr(κ -hqca)(coe)(py)] (5). A mixture of [IrH(κ -hqca)(coe)(py)]
2
2
): δ 172.88 (CO),
(4; 0.120 g, 0.211 mmol) and N-bromosuccinimide (0.075 g, 0.422
165.89 (C-8), 162.30 (C-2) (hqca), 154.96 (cis-2-Mepy), 148.30
6
927
dx.doi.org/10.1021/om400768n | Organometallics 2013, 32, 6918−6930