3716 Organometallics, Vol. 20, No. 17, 2001
O’Connor et al.
H3PO4. Mass spectra were obtained at the University of
California Riverside Mass Spectroscopy Facility.
26.1 Hz), 27.2 (d, J ) 29.3 Hz), 13.8. Anal. Calcd for
[C57H57O9P3Ir]BF4: C, 54.42; H, 4.57. Found: C, 54.35; H, 4.60.
[{CH3C(CH2P P h 2)3}Ir (C6R4H)H]BF 4 (6-H, R ) CO2CH3).
A 50 mL round-bottom flask was charged with 1 (530 mg, 0.47
mmol), AgBF4 (100 mg, 0.51 mmol), and CH2Cl2 (20 mL). After
20 min at room temperature the slurry was blanketed under
an atmosphere of ethyne and stirred an additional 6 h. The
solvent was removed in vacuo and CHCl3 (30 mL) added to
the residue. Filtration through Celite, concentration of the
filtrate to ca. 10 mL, and addition of Et2O (30 mL) gave a
precipitate, which was collected by filtration and washed with
Et2O to give 6-H (490 mg, 88% yield) as a white powder, mp
170 °C dec. IR (KBr): 1735 (s), 1602 (s), 1436 (vs), 1389 (s),
1278 (vs), 1235 (s), 1095 (vs), 1060 (vs) cm-1. 1H NMR (CDCl3,
300 MHz): δ 7.49 (m, 8H), 7.26-7.96 (m, 19 H), 6.59 (m, 4H),
3.94 (s, 3H), 3.80 (s, 3H), 3.77 (s, 3H), 3.66 (s, 3H), 2.93 (m,
4H), 2.47 (dm, J ) 15.6 Hz, 2H), 1.88 (br s, 3 H), -7.93 (dt, J
) 134.4, 11.5 Hz, 1H). 13C{1H} NMR (CDCl3, 121.7 MHz): δ
183.5 (d, J ) 6.1 Hz), 169.2 (dt, J ) 83.16, 5.34 Hz), 167.4,
166.0, 137.9, 136.5 (d, J ) 2.3 Hz), 134.8 (d, J ) 4.7 Hz), 133.4
(dd, J ) 42.7, 4.6 Hz), 132.3 (d, J ) 9.2 Hz), 132.2 (d, J ) 9.9
Hz), 132.0 (d, J ) 43.5 Hz), 132.0 (d, J ) 9.9 Hz), 131.7 (d, J
) 36.6 Hz), 131.2 (br s), 131.0 (d, J ) 9.9 Hz), 130.9 (br s),
130.8 (d, J ) 10.6 Hz), 130.8 (br s), 130.5 (d, J ) 1.5 Hz), 130.4
(br s), 130.0 (br s), 129.2 (d, J ) 9.9 Hz), 128.8 (d, J ) 9.9 Hz),
128.6 (J ) 9.9 Hz), 128.2 (d, J ) 11.4 Hz), 128.5-127.8 (m, 9
peaks), 124.1, 56.8, 52.9 (t, J ) 3.1 Hz), 52.8, 52.5, 40.3 (t, J
) 4.2 Hz), 38.3 (q, J ) 10.7 Hz), 31.8 (dd, J ) 38.9, 9.9 Hz),
30.9 (dd, J ) 27.1, 7.3 Hz), 28.0 (dd, J ) 29.4, 4.2 Hz). Anal.
Calcd for [C55H53O8P3Ir]BF4: C, 54.42; H, 4.40. Found: C,
54.02, H, 4.35. LRMS (FAB) m/z calcd for C55H53O8P3Ir 1127;
found 1127.
[{CH3C(CH2P P h2)3}Ir(CRdCRCRdCR)Cl](1,R )CO2CH3).
A 100 mL round-bottom flask was charged with (PPh3)2Ir(CRd
CRCRdCR)Cl (R ) CO2Me; 1.0 g, 0.96 mmol), [CH3C(CH2-
PPh2)3] (0.75 g), and toluene (20 mL). The reaction mixture
was refluxed for 24 h, during which time the opaque orange
solution turned to a clear pale yellow color and a cream-colored
precipitate formed. The precipitate was collected by filtration
and washed with Et2O to give 1 (1.1 g, 95% yield) as a white
1
solid, mp 266-276 °C. H NMR (CDCl3, 300 MHz): δ 7.88-
6.69 (m, 30H), 3.70 (s, 6H), 2.86 (m, 4H), 2.52 (s, 6H), 2.33 (m,
2H), 1.59 (s, 3H). 13C{1H} NMR (CDCl3, 75.5 MHz): δ 172.4,
167.7, 149.7 (br s), 137.8 (br s), 136.3 (d, J ) 56.4 Hz), 134.0
(br s), 132.3 (d, J ) 8.1), 132.2 (t, J ) 4.9), 129.8 (br s), 129.4
(br s), 128.8 (br s), 128.5 (d, J ) 10.2), 127.9 (t, J ) 4.9), 127.4
(t, J ) 4.6), 51.5, 50.2, 39.7 (m), 38.2 (br s), 35.3 (m), 31.0 (m).
Anal. Calcd for C53H51O8P3IrCl: C, 56.01; H, 4.52. Found: C,
55.89; H, 4.60.
[{CH3C(CH2P P h 2)3}Ir (CRdCRCRdCR)(NCMe)]BF 4 (3,
R ) CO2CH3). A 50 mL round-bottom flask was charged with
1 (125 mg, 0.11 mmol), AgBF4 (23 mg, 0.12 mmol), and CH3-
CN (25 mL). After stirring the solution at room temperature
(3 h), the volatiles were removed in vacuo and CH2Cl2 (20 mL)
was added to the residue to give a slurry. The mixture was
filtered through Celite and concentrated to ca. 5 mL. Addition
of Et2O gave a precipitate, which was washed with Et2O and
dried in vacuo to give 3 (113.9 mg, 88% yield) as a pinkish
white solid, mp 191 °C dec. IR (KBr): 1731 (vs), 1696 (vs),
1434 (vs), 1212 (vs), 1061 (vs) cm-1 1H NMR (CDCl3, 500
.
[{CH3C(P P h 2CH2)3}Ir {C6R4(CH2OCH3)}H]BF 4 (6-CH2O-
Me, R ) CO2CH3). A 100 mL round-bottom flask was charged
with 3 (305 mg, 0.24 mmol) and CH2Cl2 (50 mL). Methyl
propargyl ether (0.21 mL, 2.4 mmol) was added via syringe
and the solution stirred at room temperature for 18 h. The
red solution was then filtered through Celite, concentrated in
vacuo, and chromatographed (silica gel, 5% MeOH/CHCl3) to
give 189.3 mg of a red powder. Recrystallization (THF/Et2O)
in the drybox gave 6-CH2OMe (50 mg, 16% yield) as tan solid,
mp 196-198 °C. IR (KBr): 1737 (s), 1597 (s), 1440 (s), 1230
(s) cm-1. 1H NMR (CDCl3, 400 MHz): δ 7.80 (dd, J ) 10.8, 7.6
Hz, 2H), 7.60 (dd, J ) 11.2, 8.0 Hz, 2H), 7.48-7.40 (m, 3H),
7.29-7.18 (m, 9H), 7.12-7.01 (m, 6H), 6.88-6.80 (m, 6H), 6.39
(dd, J ) 12.4, 8.4 Hz, 2H), 3.99 (d, J ) 10.8 Hz, 1H), 3.89 (s,
3H), 3.86 (s, 3H), 3.72 (s, 3H), 3.21 (s, 3H), 3.18-3.14 (m, 1H),
2.96, (d, J ) 10.4 Hz, 1H), 2.92 (m, 1H), 2.86-2.68 (m, 3H),
2.65 (s, 3H), 2.24 (dd, J ) 16, 8.8 Hz, 1H), 1.87 (d, J ) 2.8 Hz,
3H), -8.69 (ddd, J ) 140.0, 13.6, 9.6 Hz, 1H). 13C{1H} NMR
(CDCl3, 100 MHz): δ 183.41 (d, J ) 7.3 Hz), 174.86, (d, J )
76.9 Hz), 167.59, 167.07, 165.59, 146.16, 137.65 (d, J ) 5.9
Hz), 135.53, 133.07 (d, J ) 4.6 Hz), 132.93 (d, J ) 5 Hz), 132.66
(d, J ) 4.1 Hz), 132.48, 132.39, 132.06 (d, J ) 9.1 Hz), 131.80
(d, J ) 9.1 Hz), 131.62 (m), 131.34 (d, J ) 2.7 Hz), 131.15,
131.04 (m), 130.72 (d, J ) 2.7 Hz), 130.45, 130.15 (m), 129.89
(d, J ) 13.7 Hz), 129.87 (d, J ) 2.3 Hz), 129.64, 129.59, 129.43,
129.42 (d, J ) 9.6 Hz), 128.95 (d, J ) 9.1 Hz), 128.73, 128.62
(d, J ) 1 Hz), 128.50, 128.42 (d, J ) 10.5 Hz), 127.71 (m),
127.10 (m), 124.97, 77.66, 57.89, 56.50, 53.07, 52.77, 52.33,
40.25 (d, J ) 3.6 Hz), 38.18 (m), 37.61 (m), 30.81 (d, J ) 27.8
Hz), 26.85 (d, J ) 29.6 Hz). Anal. Calcd for C57H57O9P3IrBF4:
C, 54.42; H, 4.57. Found: C, 53.94; H, 4.36. HRMS (FAB) m/z
calcd for C57H57O9P3Ir (M+) 1169.2794; found 1169.2822.
[{CH3C(P P h 2CH2)3}Ir {5,6,7-tr i(ca r bom eth oxy)p h th a l-
id yl}H]BF 4 (7-H, R ) CO2CH3). A 100 mL round-bottom flask
was charged with 1 (250 mg, 0.22 mmol), AgBF4 (47 mg, 0.24
mmol), and CHCl3 (30 mL). After 15 min at room temperature,
propargyl alcohol (64 µL, 1.09 mmol) was added via syringe
and the reaction stirred for an additional 40 h. The solvent
was removed and the residue dried in vacuo for 2 h. CHCl3
MHz): δ 8.00 (m, 4H), 7.59 (t, J ) 8.5 Hz, 4H), 7.49 (m, 6H),
7.36-7.29 (m, 6H), 7.16 (m, 2H), 6.83 (t, J ) 7.2 Hz, 4H), 6.23
(dd, J ) 11.0, 8.0 Hz, 4H), 3.76 (s, 6H), 3.08-3.02 (m, 4H),
2.67 (s, 6H), 2.09 (m, 2H), 2.06 (s, 3H), 1.71 (d, J ) 2.5 Hz,
3H). 13C{1H} NMR (CDCl3, 125.7 MHz): δ 173.0, 166.5 (d, J
) 3.0 Hz), 149.6 (m), 149.0 (m), 148.3 (m), 133.9 (d, J ) 59.5
Hz), 133.2 (br s), 132.8 (t, J ) 5.0 Hz), 132.0 (d, J ) 8.4 Hz),
131.9 (d, J ) 51.2 Hz), 131.1 (d, J ) 9.2 Hz), 130.1, 129.5 (d,
J ) 10.7 Hz), 128.8 (br s), 128.5 (t, J ) 4.97 Hz), 127.6 (d, J )
48.9 Hz), 52.0, 51.0, 38.6 (br s), 38.4 (q, J ) 11.5 Hz), 34.9
(m), 27.7 (br d, J ) 45.9 Hz), 3.7. Anal. Calcd for C55H54O8P3-
NIrBF4: C, 53.75; H, 4.43. Found: C, 53.92; H, 4.71.
[{CH3C(CH2P P h 2)3}Ir {C6R4(OCH2CH3)}H]BF 4 (6-OEt, R
) CO2CH3). A 25 mL round-bottom flask was charged with 1
(300 mg, 0.26 mmol), AgBF4 (56 mg, 0.29 mmol), and CHCl3
(15 mL). After 15 min at room temperature, ethyl ethynyl ether
(127 mL, 1.30 mmol) was added via syringe and the solution
was stirred for 11 h. The solvent was removed in vacuo, and
CHCl3 (40 mL) was added to give a slurry, which was filtered
through Celite. The solution was concentrated to ca. 5 mL,
and addition of Et2O (30 mL) led to precipitation of a pale
yellow solid. The powder was collected by filtration and washed
with Et2O to give 6-OEt (270 mg, 82% yield) as a yellow
powder. An analytically pure sample was obtained by chro-
matography (2000µ silica gel plate, 20% acetone/CH2Cl2; Rf )
0.6), mp 180 °C dec. IR (KBr): 1734 (s), 1600 (s), 1436 (s), 1383
1
(s), 1228 (vs) cm-1. H NMR (CDCl3, 300 MHz): δ 7.76 (ddd,
J ) 24.9, 11.1, 8.4 Hz, 4H), 7.43-7.05 (m, 20 H), 6.92 (t, J )
9.0 Hz, 2H), 6.66 (m, 4H), 3.89 (s, 3H), 3.86 (s, 3H), 3.82 (q, J
) 6.9 Hz, 2H), 3.69 (s, 3H), 3.42 (s, 3H), 3.27-2.33 (m, 6H),
1.79 (s, 3H), 0.31 (t, J ) 6.9 Hz, 3H), -8.57 (ddd, J ) 139.7,
12.6, 10.2 Hz, 1H). 13C{1H} NMR (CDCl3, 125.7 MHz): δ 167.5,
166.8, 165.5, 162.7, 134.1 (m), 133.9 (m), 133.4 (m), 133.1 (m),
132.9 (d, J ) 9.6 Hz), 132.4 (d, J ) 7.8 Hz), 132.2 (d, J ) 10.9
Hz), 132.0 (d, J ) 9.7 Hz), 131.6, 131.5, 131.3 (br s), 131.2,
131.0 (m), 130.9 (m), 130.7 (br s), 130.6 (m), 130.4 (br s), 130.2,
128.7 (d, J ) 10.1 Hz), 128.5 (d, J ) 10.9 Hz), 128.1 (d, J )
11.4 Hz), 127.5 (d, J ) 11.4 Hz), 125.8, 68.9, 56.4, 53.0, 52.7,
52.5, 40.5, 38.6 (dd, J ) 71.2, 10.5 Hz), 38.6 (m), 31.6 (d, J )