Inorganic Chemistry
Article
concentrated. The product solution was layered with diethyl ether and
allowed to stand for 5 h to begin crystallization, and then refrigerated
at −30 °C overnight. Light yellow crystals were filtered, washed lightly
with diethyl ether, and allowed to dry in the glovebox atmosphere
133.89, 124.02, 120.85, 120.49, 118.55, 88.95, 21.97, 8.88, −15.95.
+
+
HRMS (ESI ) m/z: [M] found (theory) for C H NIr, 511.1855
2
3
28
+
(511.1852); [M − CH ] found (theory) for C H NIr, 496.1628
3
22 25
(496.1617). Anal. found (calcd) for C H NIr: C, 54.16 (54.09); H,
2
3
28
(
193 mg, 77.5% yield). The product was not subject to drying under
5.41 (5.53); N 2.93 (2.74).
vacuum as a precaution against loss of potentially fugitive CH CN
ligand. This intermediate compound was used promptly without
2′
37
3
Cp*Ir(1-phenylisoquinolinato-N^C )Cl. In a minor modifica-
tion to the method reported by Li et al. for the 2-phenylpyridine
further purification for subsequent synthesis.
analog, [Cp*Ir(Cl)(μ-Cl)]2 (357 mg, 0.448 mmol), 1-phenyl-
isoquinoline (202 mg, 0.984 mmol), and NaOAc (210 mg) were
placed in a 100 mL round-bottom flask, and 20 mL of CH Cl was
′
[
C p * I r ( 2 - ( p - t o l y l ) p y r i d i n a t o - N ^ C 2 ) ( 2 , 6 -
dimethylphenylisocyanide)][PF ]. [Cp*Ir(2-(p-tolyl)pyridinato-
6
2
2
2
′
added. After stirring about 10 min, the orange solution began to turn
N^C )(NCCH )][PF ] (85 mg, 0.125 mmol) was dissolved in 5
3
6
red and the remaining [Cp*Ir(Cl)(μ-Cl)] appeared to be taken into
mL of CH CN in a 50 mL round-bottom flask. 2,6-Dimethylpheny-
2
3
solution. Stirring was continued overnight. The slurry was filtered and
lisocyanide (25 mg, 0.191 mmol) was added as a solid to the reaction
flask and quickly dissolved. Stirring was continued overnight. The
reaction solution was concentrated, layered with diethyl ether, and
refrigerated overnight at −30 °C. Pale yellow crystals and powder
rinsed through celite with additional CH Cl . The red solution was
2
2
concentrated, layered with diethyl ether, and allowed to stand for 2 h
while crystallization began. The product mixture was then refrigerated
overnight at −30 °C to promote additional precipitation. The
resulting red crystals were filtered, washed with diethyl ether, and
were filtered, washed with diethyl ether, and dried (85 mg, 84%
1
yield). H NMR (400 MHz, CD Cl ) δ 8.58 (d, J = 5.9 Hz, 1H), 7.93
2
2
1
dried under vacuum (465 mg; 91.5% yield). H NMR (400 MHz,
(
(
(
1
1
d, J = 3.8 Hz, 2H), 7.69 (d, J = 8.0 Hz, 1H), 7.46 (s, 1H), 7.31−7.23
13
CD Cl ): δ 8.95−8.89 (m, 1H), 8.59 (d, J = 6.3 Hz, 1H), 8.30 (d, J =
2
2
m, 1H), 7.16−7.07 (m, 2H), 7.02 (d, J = 7.6 Hz, 2H). C NMR
176 MHz, CD Cl ): δ 167.80, 153.24, 150.01, 142.73, 142.27,
8
=
.1 Hz, 1H), 7.92 (d, J = 6.3 Hz, 2H), 7.76−7.69 (m, 2H), 7.46 (d, J
2
2
6.3 Hz, 1H), 7.21 (t, J = 7.5 Hz, 1H), 7.13 (t, J = 7.3 Hz, 1H), 1.67
40.00, 137.37, 135.19, 129.62, 129.41, 128.28, 127.26, 126.01,
1
3
+
(s, 15H). C NMR (176 MHz, CD
2
Cl2): δ 168.28, 167.89, 146.18,
144.92, 137.47, 137.02, 131.36, 130.90, 130.07, 128.40, 127.68,
27.26, 126.53, 122.18, 121.20, 89.57, 9.27.
HRMS (ESI ) m/z: [M − Cl] found (theory) for C25
32.1621 (532.1617). Anal. found (calcd) for C H NIrCl: C, 52.90
25.30, 123.90, 120.45, 97.57, 21.67, 18.20, 9.25. HRMS (ESI ) m/z:
+
[
M − PF ] found (theory) for C H N Ir, 627.2355 (627.2353).
6
31 34
2
1
5
Anal. found (calcd) for C H N IrPF : C, 48.05 (48.24); H, 4.48
3
1
34
2
6
+
+
−
1
H25NIr,
(
4.44); N 3.53 (3.63). ν(CN): 2149 cm .
2
5
25
2
′
[
Cp*Ir(2-(p-tolyl)pyridinato-N^C )(3,5-dimethylimidazol-2-
(
52.94); H, 4.45 (4.44); N 2.48 (2.47).
2
′
ylidene)][PF ]. [Cp*Ir(2-(p-tolyl)pyridinato-N^C )(NCCH )]-
2′
6
3
[
Cp*Ir(1-phenylisoquinolinato-N^C )(NCCH )][PF ]. Cp*Ir-
3
6
[
PF ] (111 mg, 0.163 mmol), 1,3-dimethylimidazolium iodide (38
6
2
′
(
1-phenylisoquinolinato-N^C )Cl (303 mg, 0.534 mmol) was placed
in a 100 mL round-bottom flask and partly dissolved with CH CN (4
mL). AgPF (150 mg, 0.593 mmol) was dissolved in CH CN (2 mL)
and added dropwise to the stirring reaction mixture of Cp*Ir(1-
mg, 0.170 mmol), and Ag O (21 mg, 0.0906 mmol) were combined
2
in a glass reaction tube. CH Cl was added, and stirring in the dark
3
2
2
was continued overnight. The mixture was filtered through celite, and
the pale yellow solution was concentrated to about 2 mL. An
approximately equal volume of THF was added while stirring. The
mixture was layered with diethyl ether and allowed to stand for 2 h
during which time precipitation began. The mixture was refrigerated
at −30 °C overnight. Yellow powder was filtered, washed with diethyl
ether, and dried (88 mg, 73.4% yield). A second crop of 9 mg was
obtained by concentrating the supernatant to dryness, redissolving in
a minimal amount of THF and layering with diethyl ether to
6
3
2
′
phenylisoquinolinato-N^C )Cl. A white precipitate appeared as the
2′
remaining red crystals of Cp*Ir(1-phenylisoquinolinato-N^C )Cl
were gradually taken into solution. Stirring was continued an
additional 2 h. The mixture was filtered through celite, and the
orange solution was concentrated. The product solution was layered
with diethyl ether and allowed to stand for 2 h to begin crystallization,
and then refrigerated at −30 °C overnight. The resulting orange
crystals were filtered, washed lightly with diethyl ether, and allowed to
dry in the glovebox atmosphere (346 mg, 90.2% yield). The product
was not subject to drying under vacuum as a precaution against loss of
1
precipitate. H NMR (400 MHz, CD Cl ): δ 8.74 (d, J = 5.9 Hz, 1H),
2
2
7
.74−7.76 (m, 3H), 7.52 (d, J = 7.9 Hz, 1H), 7.20−7.12 (m, 1H),
6
.96 (d, J = 7.9 Hz, 1H), 6.77 (s, 2H), 3.44 (s, 6H), 2.46 (s, 3H), 1.73
(
s, 15H). 13C NMR (101 MHz, CD Cl ): δ 173.07, 169.01, 156.72,
2 2
potentially fugitive CH CN ligand. This intermediate compound was
used promptly without further purification for further synthesis.
3
1
53.74, 147.10, 143.32, 140.03, 139.24, 138.70, 125.10, 124.32,
+
1
24.29, 121.96, 119.84, 92.93, 39.24, 21.95, 9.17. HRMS (ESI ) m/z:
2
′
+
[ C p * I r ( 1 - p h e n y l i s o q u i n o l i n a t o - N ^ C ) ( 2 , 6 -
dimethylphenylisocyanide)][PF ]·Diethyl Ether. [Cp*Ir(1-phe-
[
M − PF ] found (theory) for C H N Ir, 592.2313 (592.2305).
6
27 33
3
6
Anal. found (calcd) for C H N IrPF : C, 43.73 (44.02); H, 4.44
2
7
33
3
6
2
′
(
4.51); N 5.56 (5.70).
nylisoquinolinato-N^C )(NCCH
3
)][PF ] (60 mg, 0.0836 mmol)
in a 50 mL round-bottom flask. 2,6-
2
6
2
′
was dissolved in 1 mL of CH Cl
2
Cp*Ir(2-(p-tolyl)pyridinato-N^C )(CH ). In a minor modifica-
3
38
Dimethylphenylisocyanide (13 mg, 0.0991 mmol) was dissolved in 1
mL of CH Cl and added dropwise to the stirring reaction solution.
Stirring was continued for 4 h. The reaction solution was layered with
diethyl ether and let stand 5 h at room temperature. A pale orange
precipitate formed and was washed with diethyl ether and dried (48
tion to the method reported by Park-Gehrke et al. for the 2-
phenylpyridine analog, a 50 mL Schlenk flask was charged with
Cp*Ir(tpy)Cl (39.1 mg, 0.074 mmol), 20 mL of THF, and a stir bar
2
2
inside an N glovebox. The flask was sealed with a septum, brought
2
out of the glovebox, and cooled to −78 °C, and 150 μL methyl
1
mg, 71.1% yield). H NMR (400 MHz, CD Cl ): δ 8.95 (d, J = 8.3
2
2
lithium solution (1.6 M in Et O, 0.24 mmol, 3.2 equiv) was added by
2
Hz, 1H), 8.47 (d, J = 6.4 Hz, 1H), 8.41 (d, J = 7.2 Hz, 1H), 8.05 (d, J
7.2 Hz, 1H), 7.92−7.84 (m, 2H), 7.83−7.79 (m, 1H), 7.63 (d, J =
syringe. The reaction was allowed to warm to room temperature over
which the solution darkened from yellow to a reddish-brown. The
solvent was removed in vacuo, and the product was extracted with 2 ×
=
6
.5 Hz, 4H), 7.41−7.31 (m, 2H), 7.14−7.07 (m, 1H), 7.00 (d, J = 7.6
13
Hz, 2H), 1.94 (s, 6H), 1.91 (s, 15H). C NMR (176 MHz, CD Cl2):
2
2
0 mL of pentane and filtered under N to separate remaining salts.
2
δ 168.61, 153.15, 146.36, 145.18, 137.91, 137.47, 135.25, 132.87,
31.95, 131.35, 129.69, 129.48, 128.27, 128.12, 127.24, 126.88,
26.66, 124.88, 122.79, 97.94, 18.32, 9.35. HRMS (ESI ) m/z: [M −
PF ] found (theory) for C H N Ir, 663.2356 (663.2353). Anal.
The air-stable filtrate was dried by rotary evaporation. Layering water
1
1
under a solution of the product in CH CN at 4 °C produced bright
+
3
1
red crystals (17.6 mg, 0.034 mmol, 47% yield). H NMR (600 MHz,
+
6
34 34
2
CDCl ): δ 8.45 (d, J = 5.9 Hz, 1H), 7.77 (d, J = 8.1 Hz, 1H), 7.65 (d,
3
found (calcd) for C H N IrPF ·C H O: C, 51.42 (51.75); H, 4.75
3
4
34
2
6
4
10
J = 7.8 Hz, 1H), 7.50 (ddd, J = 8.4, 7.3, 1.5 Hz, 1H), 7.42 (s, 1H),
−1
(
5.02); N 3.15 (3.11). ν(CN): 2140 cm .
6
.85 (dd, J = 7.9, 1.7 Hz, 1H), 6.81 (ddd, J = 7.3, 5.7, 1.4 Hz, 1H),
2
′
1
3
[Cp*Ir(1-phenylisoquinolinato-N^C )(3,5-dimethylimida-
2
.46 (s, 3H), 1.77 (s, 15H, Cp*), −0.28 (s, 3H, IrCH ). C NMR
3
2
′
(
151 MHz, CDCl ): δ 169.37, 166.63, 150.67, 140.36, 139.19, 135.46,
zol-2-ylidene)][PF ]. [Cp*Ir(1-phenylisoquinolinato-N^C )-
3
6
L
Inorg. Chem. XXXX, XXX, XXX−XXX