Denis Sinou et al.
FULL PAPERS
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11.3 Hz), 134.5 2d, JP, C 101.7 Hz), 158.4 2d, JP, C 16.9 Hz);
31P NMR 2DMSO-d6): d 28.5 2s).
removing of the upper phase, the solid was collected and dried
under vacuum to give the corresponding iridium complex.
trans-[IrClꢀCO){PꢀC6H4-p-OCH3)3}2] ꢀ15): yield: 90%; m.p.
178 ± 1808C; IR 2KBr): nCO 1950 cmÀ1 2s); 1H NMR 2CDCl3):
d 3.83 2s, 18H, CH3), 6.93 2d, J 8.4 Hz, 12H, Harom), 7.64 ±
7.70 2m, 12H, Harom); 31P NMR 2CDCl3): d 20.8 2s); FAB-MS:
Tris[3,5-diꢀ1H,1H-perfluorooctoxy)phenyl]phosphane
m/z 960 [M] , 932 [M ± CO] , 895 [M ± CO ± Cl ± H] .
trans-[IrClꢀCO){PꢀC6H4-m-OCH3)3}2] ꢀ16): yield: 93%;
m.p. 146 ± 1488C; IR 2KBr): nCO 1959 cmÀ1 2s); 1H NMR
2CDCl3): d 3.75 2s, 18H, CH3), 6.97 ± 7.01 2m, 12H, Harom),
7.25 ± 7.29 2m, 6H, Harom), 7.33 ± 7.36 2m, 6H, Harom), 31P NMR
Oxide ꢀ14)
A mixture of crude hydroxyphosphane oxide 13 2530 mg,
1.41 mmol), 1H,1H-perfluorooctyl nonabutanesulfonate
27.71 g, 11.3 mmol), and Cs2CO3 24.63 g, 14.2 mmol) in DMF
230 mL) was stirred at 808C under N2 for 16 h. The suspension
was then cooled at room temperature, the solution was treated
with H2O 215 mL) and diethyl ether 225 mL). D-100 was added
25 mL) and the solution was vigorously stirred for 5 min. The
ether and fluorous layers were separated, and the aqueous
layer was extracted with a 5:1 mixture of diethyl ether/D-100
22 Â 25 mL). The combined organic phases were washed with a
saturated aqueous solution of NaCl 24 Â 10 mL), and dried
over Na2SO4. Evaporation of the solvent gave a residue that
was purified by column chromatography on silica gel using a
2:1 mixture of CH2Cl2/diethyl ether as the eluent to give the
perfluorophosphane oxide 14; yield: 1.2 g 232%); Rf 0.7
2CH2Cl2/diethyl ether, 2:1); m.p. 89 ± 918C; 1H NMR
2CDCl3): d 12.6 2s); FAB-MS: m/z 960 [M] , 932 [M ±
CO] .
trans-[IrClꢀCO){PꢀC6H4-o-OCH3)3}2] ꢀ17): yield: 86%; m.p.
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205 ± 2078C. ± IR 2cmÀ1, KBr): nCO 1941 cmÀ1 2s); H NMR
2CDCl3): d 3.50 2s, 18H, CH3), 6.78 ± 6.80 2m, 6H, Harom),
6.86 ± 6.90 2m, 9H, Harom), 7.29 ± 7.33 2m, 9H, Harom); 31P NMR
2CDCl3): d 14.6 2s); FAB-MS: m/z 925 [M ± Cl] , 895 [M ±
CO ± Cl ± H] .
trans-[IrClꢀCO){PꢀC6H4-p-OCH2C7F15)3}2] ꢀ18): yellow
powder; yield: 84%; m.p. 167 ± 1698C; IR 2KBr): nCO
1961 cmÀ1 2s); 1H NMR 2CDCl3/Cl2CFCF2Cl): d 4.50 2t,
JH,F 13 Hz, 12H, CH2), 6.94 ± 7.20 2m, 12H, Harom), 7.60 ±
7.70 2m, 12H, Harom); 31P NMR 2CDCl3/Cl2CFCF2Cl): d 21.6
2s);19F NMR 2CDCl3/Cl2CFCF2Cl):d À127.0 2s, 12F), À123.8
2s, 12F), À123.6 2s, 12F), À122.9 2s, 24F), À120.3 2s, 12F),
À 82.4 2t, JF,F 9.4 Hz, 18F); FAB-MS: m/z 3102 [M ± Cl ±
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2CDCl3): d 4.46 2t, JH,F 12.6 Hz, 12H, CH2), 6.78 2t,
4JH,H 2.2 Hz, 3H, Harom), 6.92 2dd, 4JH,H 2.2, 3JH,P 13.2 Hz,
6H, Harom); 31P NMR 2CDCl3): d 29.1 2s); 19F NMR 2CDCl3):
d À 126.8 2bs, 12F), À 123.7 2bs, 12F), À 123.4 2bs, 12F),
CO ± H] .
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À 122.6 2bs, 24F), À 120.0 2bs, 12F), À 81.6 2t, JF,F 10.3 Hz,
trans-[IrClꢀCO){PꢀC6H4-m-OCH2C7F15)3}2] ꢀ19): green
18F); HRMS 2FAB): calcd. for C66H22F90O7P [M H] :
powder; yield: 85%; m.p. 106 ± 1088C; IR 2KBr): nCO
2666.9666; found: 2666.9667
1962 cmÀ1 2s); 1H NMR 2CDCl3/Cl2CFCF2Cl): d 4.39 2t,
JH,F 12.8 Hz, 12H, CH2), 7.03 ± 7.08 2m, 6H, Harom), 7.31 ±
7.40 2m, 12H, Harom), 7.44 ± 7.48 2m, 6H, Harom); 31P NMR
2CDCl3/Cl2CFCF2Cl): d 26.8 2s); 19F NMR 2CDCl3/
Cl2CFCF2Cl): d À 126.9 2s, 12F), À 123.7 2s, 12F), À 123.4
Tris[3,5-diꢀ1H,1H-perfluorooctoxy)phenyl]phosphane
ꢀ9)
2s, 12F), À 122.7 2s, 24F), À 120.1 2s, 12F), À 82.1 2t, JF,F
9.9 Hz, 18F); FAB/MS: m/z 3190 [M Na] , 3102 [M ± Cl ±
HSiCl3 230 mL, 300 mmol) was cautiously added under argon at
08C to a mixture of phosphane oxide 14 2200 mg, 75 mmol) and
freshly distilled triethylamine 244 mL, 0.32 mmol) in dry
toluene 25 mL). The mixture was warmed to 1308C and stirred
for 5 h. After being cooled to 08C, the solution was treated with
precooled deaerated 2 N NaOH 210 mL). The aqueous layer
was extracted with deaerated Et2O 22 Â 15 mL), and the
combined organic layers were washed with deaerated water
220 mL) and dried over Na2SO4. Evaporation of the solvent
gave fluorous phosphane 9 as a white solid; yield: 160 mg
CO ± H] .
trans-[IrClꢀCO){PꢀC6H4-o-OCH2C7F15)3}2] ꢀ20): green
powder; yield: 71%; m.p. 111 ± 1138C; IR 2KBr): nCO
1950 cmÀ1 2s); 1H NMR 2CDCl3/Cl2CFCF2Cl): d 4.40 2t, JH,F
14.0 Hz, 12H, CH2), 6.82 ± 6.86 2m, 6H, Harom), 7.00 ± 7.08 2m,
12H, Harom), 7.35 ± 7.41 2m, 6H, Harom); 31P NMR 2CDCl3/
Cl2CFCF2Cl): d 14.5 2s); 19F NMR 2CDCl3/Cl2CFCF2Cl):
d À 126.9 2s, 12F), À 123.9 2bs, 12F), À 123.4 2s, 12F),
À 122.7 2s, 12F), À 122.5 2s, 12F), À 119.8 2bs, 12F), À 81.1 2t,
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JF,F 9.2 Hz, 18F); FAB-MS: m/z 3131 [M ± Cl] , 3102 [M ±
281%); m.p. 78 ± 808C; H NMR 2CDCl3): d 4.37 2t, JH,F
12.7 Hz, 12H, CH2), 6.55 2t, 4JH,H 2.1 Hz, 3H, Harom), 6.58 2dd,
Cl ± CO ± H] , 1674 [M ± Cl ± 2c] , 1456 [2c] .
4JH,H 2.1, JH,P 8.1 Hz, 6H, Harom); 31P NMR 2CDCl3): d
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trans-[IrClꢀCO){PꢀC6H4-p-OCH2CH2CH2C8F17)3}2] ꢀ21):
yellow powder; yield: 78%; IR 2KBr): nCO 1961 cmÀ1 2s);
1H NMR 2CDCl3/Cl2CFCF2Cl): d 2.10 ± 2.16 2m, 12H, CH2),
2.26 ± 2.36 2m, 12H, CH2), 4.05 2t, J 5.6 Hz, 12H, OCH2), 6.89
2d, J 8.0 Hz, 12H, Harom), 7.43 ± 7.48 2m, 6H, Harom), 7.62 ± 7.66
2m, 6H, Harom); 31P NMR 2CDCl3/Cl2CFCF2Cl): d 21.0 2s);
19F NMR 2CDCl3/Cl2CFCF2Cl): d À 126.6 2s, 12F), À 123.9
2s, 12F), À 123.2 2s, 12F), À 122.4 2s, 24F), À 122.2 2s, 12 F), À
115.0 2s, 12 F), À 81.7 2t, JF,F 9.4 Hz, 18 F); FAB-MS: m/z
1.4 2s); 19F NMR 2CDCl3): d À 127.0 2bs, 12F), À 124.0 2bs,
12F), À 123.6 2bs, 12F), À 122.8 2bs, 24F), À 120.3 2bs, 12F),
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À 81.8 2t, JF,F 9.9 Hz, 18F); HRMS 2FAB): calcd. for
C66H22F90O6P [M H] : 2650.9894; found: 2650.9716.
Synthesis of Iridium Complexes 15 ± 21
3609 [M ± CO] , 3573 [M ± CO ± Cl ± H] , 1908 [M ± CO ± 3] .
A Schlenk tube was charged with [Ir2m-Cl)2COD)]2 215 mg,
22.3 mmol), phosphane 289.2 mmol), and C6H5CF3 24 mL)
under argon. The solution was stirred at room temperature
for 15 min, and CO was added. After 2 h, the solvent was
removed, the residue was washed with hexane 23 mL). After
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ꢁ 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
Adv. Synth. Catal. 2003, 345, 603 ± 611