A R T I C L E S
McBee et al.
(PyPyr)Ir(COD) (5). A 3 mL benzene slurry of 1 (0.060 g, 0.198
mmol) was added to a stirred, room-temperature solution of
[IrCl(COD)]2 (0.067 g, 2.08 mmol) in 0.5 mL of benzene. The
reaction mixture was allowed to stir at ambient temperature for
16 h, and then it was filtered. The solution was concentrated under
vacuum, and product was then crystallized by vapor diffusion of
pentane into the benzene solution at 25 °C. Three crops of crystals
were collected and dried under vacuum to afford 5 as an analytically
2 H, 3JHH ) 3.6 Hz), 8.18 (d, 1 H, 3JHH ) 4.4 Hz). 13C{1H} NMR
(C6D6, 121.7 MHz): δ 8.41, 12.26, 115.29, 118.03, 119.10, 126.43,
126.75, 127.94, 128.72, 129.65, 130.02, 132.21, 137.48, 137.97,
139.15, 139.46, 147.67 (d, JRhC ) 4.6 Hz), 151.8, 158.46. 29Si NMR
1
(via H,29Si gHMBC, C6D6, 99.3 MHz): δ 78.8 (JRhSi ) 25.3, JSiH
) 11.6 Hz, JSiH′ ) 4.8 Hz). Anal. Calcd for C33H47N2RhSi2: C,
62.83; H, 7.51; N, 4.44. Found: C, 63.17; H, 7.22; N, 4.48.
(PyPyr)Rh(H)2(SiPh3)2 (9). A 2 mL solution of HSiPh3 (0.0916
g, 0.352 mmol) was added to a solution of 3 (0.0400 g, 0.0880
mmol) in 3 mL of benzene. The reaction mixture was stirred at 25
°C for 0.5 h, and then the volatile materials were removed under
vacuum. The resulting solid was dissolved into a minimum volume
of diethyl ether, then precipitated with 3 mL of pentane at -30
°C. Precipitation was repeated three times, and the resulting solid
was dried under vacuum to afford 9 as an analytically pure red
1
pure orange solid (0.040 g, 34%). H NMR (C6D6, 500 MHz): δ
1.49 (m, 4 H, CH2), 2.10 (m, 4 H, CH2), 3.39 (m, 2 H, CH), 4.60
3
(m, 2 H, CH), 5.87 (t, 1 H, JHH ) 6.2 Hz), 6.39 (s, 1 H), 6.45 (t,
1 H, 3JHH ) 7.6 Hz), 7.08-7.25 (m, overlapping with benzene-d6),
7.29 (d, 1 H, 3JHH ) 8.4 Hz), 7.51 (d, 2 H, 3JHH ) 5.1 Hz), 7.92 (d,
2 H, 3JHH ) 7.2 Hz). 13C{1H} NMR (C6D6, 121.7 MHz): δ 30.95,
32.22, 60.75, 65.13, 117.83, 118.05, 118.66, 126.81, 127.56, 128.32,
128.77, 129.92, 130.22, 131.24, 137.58, 138.36, 138.42, 139.18,
144.99, 149.16, 160.00. Anal. Calcd for C29H27N2Ir: C, 58.47; H,
4.57; N, 4.70. Found: C, 58.28; H, 4.79; N, 4.58.
1
solid (0.0621 g, 76.8%). H NMR (C6D6, 500 MHz): δ -13.20
(dd, 1 H, JRhH ) 22.0 Hz, JHH ) 8.0 Hz, RhH), -11.90 (dd, 1 H,
JRhH ) 23.0 Hz, JHH ) 8.0 Hz, RhH), 5.77 (t, 1 H, 3JHH ) 6.4 Hz),
3
(PyPyr)Rh(CO)2 (6). A 2 mL benzene slurry of 1 (0.0385 g,
0.127 mmol) was added to a stirred solution of [RhCl(CO)2]2
(0.0247 g, 0.0635 mmol) in 2 mL of benzene. The reaction mixture
was allowed to stir at ambient temperature for 18 h, and then it
was filtered. The solution was concentrated under vacuum, and the
product was crystallized by vapor diffusion of hexane into the
benzene solution at 25 °C. Red crystals were collected and dried
under vacuum to afford 6 as red solid (0.0096 mg, 17%). 1H NMR
6.31 (s, 1 H), 6.45 (t, 1 H, JHH ) 8.4 Hz), 7.06 (m, 18 H),
7.12-7.26 (m, overlapping with benzene-d6), 7.43 (d, 2 H, 3JHH
)
7.2 Hz), 7.58 (m, 14 H). 13C{1H} NMR (C6D6, 121.7 MHz): δ
115.33, 117.68, 118.81, 126.56, 127.07, 128.54, 129.60, 129.64,
129.70, 129.81, 129.89, 130.66, 136.77, 137.14, 137.81, 138.05,
139.08, 139.64, 147.67 (d, JRhC ) 2.6 Hz), 151.80, 158.46. 29Si
NMR (via 1H,29Si gHMBC, C6D6, 99.3 MHz): δ 49.1 (JRhSi ) 22.4
Hz, JSiH ) 19.4 Hz, JSiH′ ) 7.4 Hz). Anal. Calcd for C57H47N2RhSi2:
C, 74.49; H, 5.15; N, 3.05. Found: C, 74.40; H, 5.18; N, 2.95.
3
3
(C6D6, 500 MHz): δ 5.78 (t, JHH ) 6.4 Hz, 1H), 6.42 (t, JHH
)
(PyPyr)Rh(H)2(SiPh2 Bu)2 (10). Neat HSitBuPh2 (0.0850 g,
t
7.8 Hz, 1H), 6.54 (s, 1H), 7.10-7.35 (m, overlapping with
benezene-d6), 7.51 (d, 3JHH ) 7.6 Hz, 2H), 7.63 (d, 3JHH ) 5.6 Hz,
0.354 mmol) in benzene was added to a stirred, room-temperature
solution of 3 (0.0400 g, 0.088 mmol) in 3 mL of benzene. The
reaction mixture was stirred at 25 °C for 0.5 h, and the volatile
materials were removed under vacuum. The resulting solid was
dissolved into a minimum volume of diethyl ether, and then
precipitated with 3 mL pentane at -30 °C. Precipitation was
repeated as above three times, and the resulting solid was dried
under vacuum to afford 10 as an analytically pure red solid (0.0516
mg, 66.7%). 1H NMR (C6D6, 500 MHz): δ -14.64 (dd, 1 H, JRhH
) 19.2 Hz, JHH ) 9.6 Hz, RhH), -13.02 (dd, 1 H, JRhH ) 24.4
1H), 7.72 (d, JHH ) 7.6 Hz, 2H). IR (cm-1): 2004 (CO), 2067
3
(CO).
Alternative Synthesis of (PyPyr)Rh(CO)2 (6). Carbon mon-
oxide (1 atm) was bubbled through a stirred solution of 3 (0.261 g,
0.479 mmol) in 30 mL of benzene for 1 h. The volatile material
was removed to afford 6 as an analytically pure orange solid (0.261
1
g, 99%). The H NMR spectrum is identical to that of the prior
synthesis. 13C{1H} NMR (C6D6, 121.7 MHz): δ 114.65, 117.88,
118.94, 127.02, 127.62, 128.85, 129.82, 129.68, 130.33, 132.34,
136.43, 137.89, 138.28, 138.83, 149.15 (d, JRhC ) 3.0 Hz), 151.49,
158.95, 184.94 (d, JRhC ) 70.3 Hz), 187.88 (d, JRhC ) 64.4 Hz).
Anal. Calcd for C23H15N2O2Rh: C, 60.81; H, 3.33; N, 6.17. Found:
C, 60.93; H, 3.58; N, 5.82.
3
Hz, JHH ) 9.6 Hz, RhH), 1.00 (s, 18 H, CCH3), 5.85 (t, 1 H, JHH
3
) 6.0 Hz), 6.38 (s, 1 H), 6.54 (t, 1 H, JHH ) 7.6 Hz), 7.05-7.46
3
(m, overlapping with benzene-d6), 7.53 (d, 2 H, JHH ) 8.0 Hz),
7.61 (m, 1H), 7.68 (m, 4 H), 7.75 (d, 2 H, 3JHH ) 3.2 Hz). 13C{1H}
NMR (C6D6, 121.7 MHz): δ 24.4, 29.01, 115.88, 117.64, 118.79,
126.57, 127.27, 127.64, 127.86, 128.67, 129.78, 129.98, 130.51,
136.09, 136.32, 136.77, 137.79, 138.09, 139.38, 139.77, 146.89 (d,
(PyPyr)Ir(CO)2 (7). A 3 mL benzene slurry of 1 (0.0490 g, 0.162
mmol) was added to a stirred solution of IrCl(CO)3 (0.0670 g, 2.08
mmol) in 0.5 mL of benzene. The reaction mixture was allowed to
stir at 25 °C for 26 h. The mixture was then filtered and concentrated
under vacuum. Vapor diffusion of hexane into the solution of the
1
JRhC ) 2.6 Hz), 151.24, 157.97. 29Si NMR (via H,29Si gHMBC,
C6D6, 99.3 MHz): δ 56.6 (JRhSi ) 21.8 Hz, JSiH < 0.2 Hz). Anal.
Calcd for C53H55N2RhSi2: C, 72.41; H, 6.31; N, 3.19. Found: C,
72.21; H, 6.55; N, 3.20.
1
product at 25 °C yielded red crystals of 7 (0.0085 g, 9.7%). H
3
NMR (C6D6, 500 MHz): δ 5.68 (t, JHH ) 6.2 Hz, 1H), 6.35 (t,
3JHH ) 7.4 Hz, 1H), 6.46 (s, 1H), 7.12-7.26 (m, overlapping with
benzene-d6), 7.45 (d, 3JHH ) 7.2 Hz, 2H), 7.71 (d, 3JHH ) 7.2 Hz,
(PyPyr)Ir(H)2(SiPh3)2 (11). A 2 mL benzene solution of 1
(0.0661 g, 0.223 mmol) was added to a stirred, room-temperature
suspension of [ClIr(COE)2]2 (0.1000 g, 0.112 mmol) in 2 mL of
benzene. After stirring for 15 min, solid HSiPh3 (0.179 g, 0.687
mmol) was added in portions. After stirring for 0.5 h the reaction
mixture was filtered, and the resulting solution was concentrated
under vacuum. A solid was precipitated upon addition of 2 mL of
pentane. The supernatant was removed, and the solid was dissolved
in 2 mL of benzene, and precipitation with pentane was repeated
three times. The resulting solid was dried under vacuum to afford
3
2H), 7.83 (d, JHH ) 5.6 Hz, 1H). 13C{1H} NMR (C6D6, 121.7
MHz): δ 115.39, 118.68, 118.79, 127.34, 128.31, 128.79, 128.89,
129.75, 130.75, 133.23, 137.40, 137.51, 137.74, 138.40, 149.95,
151.37, 158.66, 172.61, 178.87. Anal. Calcd for C23H15N2IrO2: C,
50.82; H, 2.78; N, 5.15. Found: C, 50.61; H, 2.83; N, 5.24. IR
(cm-1): 1986 (CO), 2050 (CO).
(PyPyr)Rh(H)2(SiEt3)2 (8). Neat HSiEt3 (0.0215 g, 0.185 mmol)
was added to a solution of 3 (0.0180 g, 0.0396 mmol) in 0.5 mL
of benzene. The reaction mixture was allowed to stir at ambient
temperature for 0.5 h, and the volatile materials were then removed
under vacuum. The resulting solid was washed with hexane (5 ×
3 mL) and dried in vacuo to afford 8 as an analytically pure red-
1
11 as an analytically pure red powder (0.149 g, 66.3%). H NMR
(C6D6, 500 MHz): δ -15.80 (d, 1 H, 2JHH ) 2.7 Hz, IrH), -13.98
(d, 1 H, 2JHH ) 2.7 Hz, IrH), 5.65 (t, 1 H, 3JHH ) 6.5 Hz), 6.24 (s,
1 H), 6.40 (t, 1 H, 3JHH ) 7.8 Hz), 7.05 (m,18 H,), 7.19-7.30 (m,
8 H), 7.39 (d, 1 H, 3JHH ) 7.5 Hz), 7.54 (d, 12 H, 3JHH ) 7.0 Hz),
1
brown solid (0.0126 g, 50.4%). H NMR (C6D6, 500 MHz): δ
3
-15.43 (dd, 1 H, JRhH ) 25.5 Hz, JHH ) 9.5 Hz, RhH), -14.64
(dd, 1 H, JRhH ) 25.0 Hz, JHH ) 9.5 Hz, RhH), 0.54 (t, 18 H,
CH3), 0.97 (q, 12 H, CH2), 6.12 (t, 1 H, 3JHH ) 5.2 Hz), 6.56 (t, 1
H, 3JHH ) 7.2 Hz), 6.63 (s, 1 H), 7.12-7.26 (m, overlapping with
benzene-d6), 7.36 (m, 4 H), 7.63 (d, 2 H, 3JHH ) 5.2 Hz), 8.00 (d,
7.72 (d, JHH ) 5.0 Hz, 2 H). 13C{1H} NMR (C6D6, 121.7 MHz):
δ 116.22, 118.64, 118.91, 126.81, 127.04, 128.35, 128.59, 128.70,
129.37, 129.72, 130.59, 135.85, 136.59, 137.35, 138.04, 138.84,
139.11, 140.21, 149.35, 152.87, 158.57.29Si NMR (via 1H,29Si
gHMBC, C6D6, 99.3 MHz): δ 8.3 (JSiH ) 1.9 Hz, JSiH′ ) 1.9 Hz).
9
12712 J. AM. CHEM. SOC. VOL. 131, NO. 35, 2009