H/D Incorporation by Cationic Iridium Complexes
A R T I C L E S
Reactions with gases were performed by addition of a known
pressure of gas from a high-vacuum line into the reaction vessel at
25 °C. The pressure was determined using a digital MKS Baratron
gauge attached to the line. Elemental analyses were performed at the
UC-Berkeley Microanalytical facility with a Perkin-Elmer 2400 Series
II CHNO/S Analyzer. Gas Chromatograph-Mass Spectroscopy
(GC-MS) data were obtained using an Agilent Technologies Instrument
6890N GC (column #HP-5MS, 30.0m × 250µm × 0.25 µm calibrated)
and 5973N MS.
Synthesis of Cp*PMe3Ir(3,5-C6H3(C(CH3)3)2)OTf (10). A 20-mL
vial was charged with 10 (0.100 g, 0.176 mmol), 1,3-di-tert-butylben-
zene (0.5 mL), 5 mL CH2Cl2, and a stirbar. The reaction mixture was
stirred at 25 °C for 20 h. The volatile materials were removed under
vacuum. The orange solid was crystallized from a concentrated Et2O
1
solution at -35 °C to yield orange crystals (0.086 g, 66%). H NMR
(400 MHz): δ 7.11 (s, 2H, Ir-(3,5-C6H3(C(CH3)3)2)), 6.93 (s, 1H, Ir-
(3,5-C6H3(C(CH3)3)2)), 1.62 (d, 15H, 4JP-H ) 1.6 Hz, C5(CH3)5), 1.49
2
(d, 9H, JP-H ) 10.4 Hz, P(CH3)3), 1.34 (s, 18H, Ir-(3,4-C6H3-
(C(CH3)3)2)). 13C{1H} NMR: δ 149.4 (s, C6H3(C(CH3)3)2), 144.4 (d,
2JP-C ) 14 Hz, i-C6H3(C(CH3)3)2), 131.1 (s, C6H3(C(CH3)3)2), 116.3
Unless otherwise indicated, NMR spectra were obtained using a
1
Bruker AVQ-400 MHz spectrometer (400 MHz for H, 162.1 MHz
2
(s, C6H3(C(CH3)3)2), 93.6 (s, JP-C ) 3 Hz, C5(CH3)5), 34.9 (s, C6H3-
for 31P{1H}, 376.5 MHz for 19F) or a DRX-500 MHz spectrometer (500
(C(CH3)3)2), 31.8 (s, C6H3(C(CH3)3)2), 14.8 (d, 1JP-C ) 38 Hz, P(CH3)3),
9.5 (s, C5(CH3)5). 31P{1H} NMR: δ -24.0 (s). 19F NMR: δ -78.0
(s). Anal. Calcd for C28H45F3IrO3PS: C, 45.33; H, 6.11. Found: C,
44.97; H, 6.10.
1
2
MHz for H, 125 MHz for 13C{1H}, 76.8 MHz for H, 99 MHz for
29Si{1H}) at 25 °C. Chemical shifts (δ) are reported in parts per million
(ppm) relative to residual protiated solvent, coupling constants are
reported in Hertz (Hz), and integrations are reported in number of
protons. 19F spectra are reported relative to CFCl3 as the external
standard and 31P{1H} spectra are reported relative to trimethyl phosphate
as the external standard. Unless otherwise noted, samples for NMR
analysis were prepared using CD2Cl2 as the solvent.
Synthesis of Cp*PMe3Ir(o-C6H4(CH3))OTf (12). A 20-mL vial was
charged with Cp*PMe3Ir(o-C6H4(CH3))Br (0.091 g, 0.157 mmol),
AgOTf (0.048 g, 0.188 mmol), 3 mL Et2O, 2 mL C6H6, and a stirbar.
The reaction mixture was stirred in the dark at 25 °C for 20 h. The
reaction mixture was filtered through Celite, and the volatile materials
were removed under vacuum. The orange solid was crystallized from
a concentrated Et2O solution at -35 °C to yield orange crystals (0.091
Synthesis of Cp*PMe3Ir(SiEt2OTf)Et (6). A 20-mL vial was
charged with 5 (0.100 g, 0.160 mmol), Et3SiH (0.028 g, 0.240 mmol),
5 mL CH2Cl2, and a stirbar. The reaction mixture was stirred at 25 °C
for 5 min. The volatile materials were removed under vacuum to yield
6 as a pale yellow solid (0.105 g, 90%). 1H NMR (500 MHz): δ 1.83
1
g, 90%). H NMR (400 MHz): δ 7.17 (d, 1H, JH-H ) 8.5 Hz, Ir-
(o-C6H4(CH3))), 7.08 (d, 1H, JH-H ) 6.8 Hz, Ir-(o-C6H4(CH3))), 6.85
(m, 2H, Ir-(o-C6H4(CH3))), 2.20 (s, 3H, Ir-(o-C6H4(CH3))), 1.62 (d,
4
2
(d, 15H, JP-H ) 2.0 Hz, C5(CH3)5), 1.51 (d, 9H, JP-H ) 10.0 Hz,
P(CH3)3) 1.27 (m, 3H, Ir-CH2CH3), 1.17 (m, 4H, SiCH2CH3), 1.05
(m, 2H, Ir-CH2CH3), 1.02 (m, 6H, SiCH2CH3). 13C{1H} NMR: δ 96.7
(s, C5(CH3)5), 21.1 (s, Ir-CH2CH3), 18.3 (d, 1JP-C ) 37.5 Hz, P(CH3)3),
14.1 (s, SiCH2CH3), 13.1 (s, SiCH2CH3), 9.9 (s, C5(CH3)5), 8.6 (s,
4
2
15H, JP-H ) 2.0 Hz, C5(CH3)5), 1.55 (d, 9H, JP-H ) 10.4 Hz,
P(CH3)3). 13C{1H} NMR: δ 148.1 (d, 2JP-C ) 12.5 Hz, i-C6H5(CH3)),
144.1 (s, (C6H4(CH3))), 138.5 (d, J ) 6.3 Hz, C6H4(CH3)), 130.8
(s, (C6H4(CH3))), 124.6 (s, C6H4(CH3)), 123.5 (s, C6H4(CH3)), 93.7 (s,
2JP-C ) 3.8 Hz, C5(CH3)5), 25.7 (s, C6H4(CH3)), 14.9 (d, 1JP-C ) 36.3
Hz, P(CH3)3), 9.8 (s, C5(CH3)5). 31P{1H} NMR: δ -21.4 (s). 19F
NMR: δ -77.6 (s). Anal. Calcd for C21H31F3IrO3PS: C, 39.18; H,
4.85. Found: C, 38.84; H, 4.76.
2
SiCH2CH3), 8.5 (s, SiCH2CH3), -18.6 (d, JP-C ) 6.3 Hz, Ir-CH2-
CH3). 31P{1H} NMR: δ -45.1 (s). 19F NMR: δ -76.8 (s). 29Si{1H}
1
NMR: δ 70.4 (d, JP-Si ) 23.9 Hz). Anal. Calcd for C20H39F3IrO3-
PSSi: C, 35.98; H, 5.89. Found: C, 35.60; H, 5.80.
Synthesis of Cp*PMe3Ir(m-C6H4(CH3))OTf (13). A 20-mL vial
was charged with Cp*PMe3Ir(m-C6H4(CH3))Cl (0.262 g, 0.494 mmol),
AgOTf (0.152 g, 0.593 mmol), 6 mL Et2O, 4 mL C6H6, and a stirbar.
The reaction mixture was stirred in the dark at 25 °C for 20 h. The
reaction mixture was filtered through Celite, and the volatile materials
were removed under vacuum. The orange solid was crystallized from
a concentrated Et2O solution at -35 °C to yield orange crystals (0.123
Synthesis of Cp*PMe3Ir(3,5-C6H3(CH3)2)OTf (8). A 20-mL vial
was charged with 10 (0.100 g, 0.176 mmol), m-xylene (0.5 mL), 10
mL CH2Cl2, and a stirbar. The reaction mixture was stirred at 25 °C
for 20 h. The volatile materials were removed under vacuum. The
orange solid was crystallized from a concentrated Et2O solution at
-35 °C to yield orange crystals (0.092 g, 80%). 1H NMR (400 MHz):
δ 6.95 (s, 2H, Ir-(3,5-C6H3(CH3)2)), 6.57 (s, 1H, Ir-(3,5-C6H3(CH3)2)),
1
g, 32%). H NMR (400 MHz): δ 7.13 (s, 1H, Ir-(m-C6H4(CH3))),
4
2.20 (s, 6H, Ir-(3,4-C6H3(CH3)2)), 1.64 (d, 15H, JP-H ) 1.6 Hz,
7.06 (d, 1H, JH-H ) 7.6 Hz, Ir-(m-C6H4(CH3))), 6.96 (t, 1H, JH-H
)
2
C5(CH3)5), 1.47 (d, 9H, JP-H ) 8.8 Hz, P(CH3)3). 13C{1H} NMR: δ
7.6 Hz, Ir-(m-C6H4(CH3))), 6.76 (d, 1H, JH-H ) 7.2 Hz, Ir-(m-C6H4-
146.1 (s, i-C6H3(CH3)2), 136.8 (s, C6H3(CH3)2), 134.2 (s, C6H3(CH3)2),
126.3 (s, C6H3(CH3)2), 93.4 (s, C5(CH3)5), 21.4 (s, C6H3(CH3)2), 14.5
(d, 1JP-C ) 50 Hz, P(CH3)3), 9.4 (s, C5(CH3)5). 31P{1H} NMR: δ -24.5
(s). 19F NMR: δ -78.0 (s). Anal. Calcd for C22H33F3IrO3PS: C, 40.17;
H, 5.06. Found: C, 39.90; H, 5.20.
4
(CH3))), 2.24 (s, 3H, Ir-(m-C6H4(CH3))), 1.63 (d, 15H, JP-H ) 2.0
2
Hz, C5(CH3)5), 1.48 (d, 9H, JP-H ) 10.4 Hz, P(CH3)3). 13C{1H}
2
NMR: δ 146.9 (d, JP-C ) 13.8 Hz, i-C6H4(CH3)), 137.5 (s, (C6H4-
(CH3))), 132.8 (s, C6H4(CH3)), 128.1 (s, (C6H4(CH3))), 127.1 (s, C6H4-
(CH3)), 123.3 (s, C6H4(CH3)), 93.6 (s, 2JP-C ) 2.5 Hz, C5(CH3)5), 21.6
(s, C6H4(CH3)), 14.6 (d, 1JP-C ) 38.8 Hz, P(CH3)3), 9.5 (s, C5(CH3)5).
31P{1H} NMR: δ -24.1 (s). 19F NMR: δ -77.4 (s). Anal. Calcd for
C21H31F3IrO3PS: C, 39.18; H, 4.85. Found: C, 39.52; H, 4.73.
Synthesis of Cp*PMe3Ir(3,5-C6H3(CH(CH3)2)2)OTf (9). A 20-mL
vial was charged with 10 (0.100 g, 0.176 mmol), 1,3-diisopropylbenzene
(0.5 mL), 5 mL CH2Cl2, and a stirbar. The reaction mixture was stirred
at 25 °C for 20 h. The volatile materials were removed under vacuum.
The orange solid was crystallized from a concentrated Et2O solution
at -35 °C to yield orange crystals (0.028 g, 24%). 1H NMR (400
MHz): δ 6.94 (s, 2H, Ir-(3,5-C6H3(CH(CH3)2)2)), 6.59 (s, 1H, Ir-
(3,5-C6H3(CH(CH3)2)2)), 2.76 (s, 2H, JH-H ) 6.8 Hz, Ir-(3,5-C6H3-
Synthesis of Cp*PMe3Ir(p-C6H4(CH3))OTf (14). A 20-mL vial was
charged with Cp*PMe3Ir(p-C6H4(CH3))Br (0.296 g, 0.512 mmol),
AgOTf (0.158 g, 0.614 mmol), 6 mL Et2O, 4 mL C6H6, and a stirbar.
The reaction mixture was stirred in the dark at 25 °C for 20 h. The
reaction mixture was filtered through Celite, and the volatile materials
were removed under vacuum. The orange solid was crystallized from
a concentrated Et2O solution at -35 °C to yield orange crystals (0.252
4
(CH(CH3)2)2)), 1.63 (d, 15H, JP-H ) 2.0 Hz, C5(CH3)5), 1.47 (d, 9H,
2JP-H ) 10.8 Hz, P(CH3)3), 1.20 (d, 12H, JH-H ) 6.8 Hz, Ir-(3,4-
C6H3(CH(CH3)2)2)). 13C{1H} NMR: δ 147.8 (s, C6H3(CH(CH3)2)2),
1
g, 77%). H NMR (400 MHz): δ 7.13 (d, 2H, JH-H ) 8.0 Hz, Ir-
2
145.5 (s, JP-C ) 13.8 Hz, i-C6H3(CH(CH3)2)2), 131.9 (s, C6H3(CH-
(p-C6H4(CH3))), 6.91 (d, 2H, JH-H ) 7.5 Hz, Ir-(p-C6H4(CH3))), 2.29
2
4
(CH3)2)2), 119.8 (s, C6H3(CH(CH3)2)2), 93.5 (s, JP-C ) 3.8 Hz,
(s, 3H, Ir-(p-C6H4(CH3))), 1.64 (d, 15H, JP-H ) 2.0 Hz, C5(CH3)5),
2
1.48 (d, 9H, JP-H ) 11.0 Hz, P(CH3)3). 13C{1H} NMR: δ 141.8 (d,
C5(CH3)5), 34.6 (s, C6H3(CH(CH3)2)2), 24.4 (s, C6H3(CH(CH3)2)2), 14.7
1
(d, JP-C ) 37.5 Hz, P(CH3)3), 9.5 (s, C5(CH3)5). 31P{1H} NMR: δ
2JP-C ) 15.0 Hz, i- C6H4(CH3)), 136.3 (s, (C6H4(CH3))), 132.0 (s, C6H4-
-24.0 (s). 19F NMR: δ -78.0 (s). Anal. Calcd for C26H41F3IrO3PS:
(CH3)), 129.1 (s, (C6H4(CH3))), 93.5 (s, JP-C ) 3.8 Hz, C5(CH3)5),
2
1
C, 43.75; H, 5.79. Found: C, 43.39; H, 5.90.
20.7 (s, C6H4(CH3)), 14.6 (d, JP-C ) 37.5 Hz, P(CH3)3), 9.5 (s,
9
J. AM. CHEM. SOC. VOL. 126, NO. 40, 2004 13041