Fluorinated Dithieno[3,2-b:2′,3′-d]phospholes
Organometallics, Vol. 28, No. 3, 2009 739
Table 2. Crystallographic Data for 2 and 4b
(5.18 mL, 12.95 mmol) was added dropwise at -78 °C. After
stirring for 40 min at the same temperature, ClSnBu3 (4.21 g, 12.95
mmol) was added at -78 °C, and the reaction mixture was further
stirred at room temperature overnight. Subsequently, the mixture
was filtered through neutral alumina, and the solvent was removed
compound
formula
2
C14H4F5PS2
362.26
4b
C29.5H11.5F9OPS2
647.98
Mr
T/K
110(2)
173(2)
1
under vacuum to afford a colorless oil (yield: 3.39 g, 65%). H
crystal system
space group
a/Å
orthorhombic
Pcab
11.0038(11)
14.7512(16)
15.7784(16)
90
90
90
2561.1(5)
8, 1.879
1440
triclinic
P-1
5
4
NMR (400 MHz, CDCl3): δ ) 6.97 (ddd, J (H-F) ) 2 Hz, J
(H-H) ) 2.4, 3J (H-F) ) 4 Hz, 2H), 6.71 (tt, 4J (H-H) ) 2.4, 3J
(H-F) ) 9.2, 1H), 1.61-1.53 (m, 6H), 1.41-1.31 (m, 6H),
1.13-1.09 (m, 6H), 0.99-0.87 (m, 6H), 0.94-0.90 (t, 9H) ppm;
13C{1H, APT} NMR (100 MHz, CDCl3): δ ) 163.3 (dt, 1J (C-F)
8.872(3)
10.929(4)
13.668(5)
76.85(2)
81.90(2)
88.95(2)
1277.5(8)
2, 1.684
649
b/Å
c/Å
R/°
ꢀ/°
2
) 255 Hz,3J (C-F) ) 5.3 Hz, 3,5-difluorophenyl), 137.8 (d, J
γ/°
V/Å3
3
(C-F) ) 6.5 Hz, 3,5-difluorophenyl), 136.6 (d, J (C-F) ) 4.3
Z, Dc/Mg cm-3
F(000)
Hz, 3,5-difluorophenyl), 115.1 (d, 2J (C-F) ) 18.8 Hz, 3,5-
difluorophenyl), 29.1, 27.4, 13.7, 9.7 ppm.
µ (Mo KR)/mm-1
θ range for data
collection
reflections collected/
unique (Rint)
data/restraints/
parameters
final R indices
[I > 2σ(I)]
R indices (all data)
0.592
2.58-30.87
0.363
3.31-27.50
Compound 4a. Compound 3 (0.71 g, 1.33 mmol) and 4-tribu-
tyltin-fluorobenzene (1.08 g, 2.80 mmol) were dissolved in THF
(35 mL). Pd(PPh3)4 (0.33 g, 0.28 mmol) and CuI (0.053 g, 0.28
mmol) were added, and the mixture was refluxed for 20 h at 120
°C. After removing the solvent under vacuum, a red oil was
obtained. The mixture was dissolved in CHCl3 and filtered over
neutral alumina. The filtrate was evaporated to dryness and washed
with pentane, affording a red solid. Compound 4a was further
purified by column chromatography (yield: 0.45 g, 60%). 31P{1H}
NMR (162 MHz, CD2Cl2): δ ) 4.35 ppm; 19F{1H} NMR (282
MHz, CD2Cl2): δ ) -113.3 (m, p-F-phenyl), -130.1 (d br, J )
20.9, o-F5C6), -146.5 (t br, J ) 20.6, p-Ph), -159.6 (m, m-Ph)
ppm; 1H NMR (400 MHz, CDCl3): δ ) 7.56 (dd, 3J (H-H) ) 8.8
19 045/3471
(0.0675)
3471/0/199
10 865/5818
(0.0490)
5818/0/392
R1 ) 0.0358,
wR2 ) 0.0939
R1 ) 0.0423,
wR2 ) 0.0965
1.014
R1 ) 0.0521,
wR2 ) 0.1123
R1 ) 0.0998,
wR2 ) 0.1368
0.988
GOF on F2
largest diff. peak
0.528 and -0.321
0.279 and -0.421
and hole/e Å3
122.9 Hz, ipso-thiophene), 130.0 (d, J (C-F) ) 4.7 Hz, 3,4-
4
3
Hz, J (H-F) ) 5.2 Hz, 4H, m-F-phenyl), 7.52 (dd, J (H-P) )
2
difluorophenyl), 123.6 (dt, J (C-F) ) 4.9 Hz,2J (C-P) ) 15.0
6
3
2.8 Hz, J (H-F) ) 5.6 Hz, 2H, thiophene), 7.13 (t, J (H-F) )
Hz, thiophene), 122.1 (dd, J (C-F) ) 3.6 Hz, J (C-P) ) 6.1 Hz,
8.8, 3J (H-H) ) 8.8 Hz, 4H, o-F-phenyl) ppm; 13C{1H, APT} NMR
2
5
thiophene), 118.3 (dd, J (C-F) ) 3.6 Hz, J (C-P) ) 6.1 Hz,
1
(100 MHz, CDCl3): δ ) 162.9 (d, J (C-F) ) 248.1 Hz, ipso-F-
2
thiophene), 116.3 (d, J (C-F) ) 17.7 Hz, 3,4-difluorophenyl),
phenyl), 147.6 (d br, 1J (C-F) ) 249.0 Hz, Ph), 147.1 (d, 2J (C-P)
) 16.1 Hz, thiophene), 145.0 (d, 2J (C-P) ) 28.1 Hz, thiophene),
115.0 (d, J (C-F) ) 18.7 Hz, 3,4-difluorophenyl) ppm. Elemental
analysis calcd (%) for C26H10F7OPS2 (602.43): C, 51.84; H, 1.34.
Found: C, 51.51; H, 1.27.
1
1
141.1 (d br, J (C-F) ) 265.4 Hz, Ph), 137.8 (d br, J (C-F) )
2
254.2 Hz, Ph), 136.5 (d, J (C-P) ) 28.1 Hz, ipso-thiophene),
Compound 4c. Compound 3 (0.73 g, 1.35 mmol) and 1,3-
difluoro-5-tributyltinbenzene (1.13 mg, 2.80 mmol) were dissolved
in THF (40 mL). Pd(PPh3)4 (0.35 g, 0.30 mmol) and CuI (0.057 g,
0.30 mmol) were added, and the mixture was refluxed for 20 h.
After removing the solvent under vacuum, a red oil was obtained.
The mixture was dissolved in CHCl3 and filtered over neutral
alumina. The filtrate was evaporated to dryness again, and washed
with pentane, affording a red solid. Compound 4c was purified by
preparative TLC (0.24 g, 30%). 31P{1H} NMR (162 MHz, CD2Cl2):
4
4
129.2 (d, J (C-F) ) 3.3 Hz, p-F-phenyl), 127.6 (d, J (C-F) )
8.2 Hz, p-F5C6), 122.8 (dt, J (C-F) ) 4.9 Hz,2J (C-P) ) 14.9
5
Hz, thiophene), 116.3 (d, 2J (C-F) ) 21.9 Hz, m-F5C6) ppm.
Elemental analysis calcd (%) for C26H10F7OPS2 (566.45): C, 55.13;
H, 1.78. Found: C, 54.69; H, 2.02.
Compound 4b. Compound 3 (0.65 g, 1.21 mmol) and 1,2-
difluoro-4-tributyltinbenzene (1.05 g, 2.60 mmol) were dissolved
in THF (40 mL). Pd(PPh3)4 (0.35 g, 0.30 mmol) and CuI (0.057 g,
0.30 mmol) were added, and the mixture was refluxed for 20 h.
After removing the solvent under vacuum, a red oil was obtained.
The mixture was then dissolved in CHCl3 and filtered over neutral
alumina. The filtrate was evaporated to dryness and washed with
pentane, affording a red solid. Compound 4b was further purified
by preparative TLC (yield: 0.43 g, 60%). Recrystallization from
toluene at room temperature afforded 4b as red single crystals
suitable for X-ray structure analysis. 31P{1H} NMR (400 MHz,
CD2Cl2): δ ) 3.98 ppm; 19F{1H} NMR (282 MHz, CDCl3): δ )
-130.2 (dm, 3J (F-F) ) 20.6, 2F, o-F5C6), -137.1 (ddd, J ) 7.8
δ ) 3.84 ppm; 19F NMR (282 MHz, CDCl3): δ ) -109.2 (t, J
3
(F-H) ) 8.178, 4F, 3,5-difluorophenyl), -130.1 (dm, 3J (F-F) )
20.9, 2F, o-F5C6), -145.9 (tm, 3J (F-F) ) 20.3, 1F, p-F5C6),
1
-159.3 (m, 2F, m-F5C6) ppm; H NMR (400 MHz, CDCl3): δ )
7.62 (dd, 6J (H-F) ) 2.4 Hz, 3J (H-P) ) 5.6 Hz, 2H, thiophene),
7.11 (dd, 4J (H-F) ) 8.0 Hz, 3J (H-H) ) 2.0 Hz, 4H,
3,5-difluorophenyl), 6.82 (tt, 3J (H-F) ) 8.8 Hz, 4J (H-H) ) 2.4
Hz, 2H, 3,5-difluorophenyl) ppm; 13C{1H, APT} NMR (100 MHz,
1
CDCl3): δ ) 164.7 (dd, J (C-F) ) 252.4 Hz,3J (C-F) ) 13.1
Hz, 3,5-difluorophenyl), 147.6 (d br, 2J (C-F) ) 252.4 Hz, o-F5C6),
3
3
2
Hz, J ) 10.9 Hz, J (F-F) ) 20.0 Hz, 2F, 3,4-difluorophenyl),
146.0 (d br, J (C-P) ) 16.0 Hz, thiophene), 145.6 (d, J (C-F)
) 27.7 Hz, thiophene), 142.1 (d br, 1J (C-F) ) 200.4 Hz, p-F5C6),
137.9 (d br, J (C-F) ) 247.3 Hz, m-F5C6), 137.2 (d, 1J (C-P) )
123 Hz, ipso-thiophene), 135.7 (d, J (C-F) ) 10.1 Hz, 3,5-
-137.8 (m, 2F, 3,4-difluorophenyl), -146.2 (ttd, 3J (F-F) ) 20.6,
4J (F-F) ) 5.6, 5J (F-P) ) 2.8, 1F, p-F5C6), -159.3 (tm, 3J (F-F)
) 27.1, 2F, m-F5C6) ppm; 1H NMR (400 MHz, CD2Cl2): δ ) 7.56
(dd, 3J (H-P) ) 2.4 Hz, 6J (H-F) ) 8.8 Hz, 2H), 7.48-7.43 (m,
2H), 7.45 (ddd, 4J (H-H) ) 2.1 Hz, 3J (H-H) ) 7.5 Hz, 3J (H-F)
5
difluorophenyl), 124.3 (dt, J (C-F) ) 5.1 Hz,2J (C-P) ) 14.9
3
2
Hz, thiophene), 108.8 (dd, J (C-F) ) 7.9 Hz, J (C-F) ) 19.2
Hz, 3,5-difluorophenyl), 104.0 (t, 2J (C-F) ) 25.3 Hz, 3,5-
difluorophenyl) ppm. Elemental analysis calcd (%) for
C26H10F7OPS2 (602.43): C, 51.84; H, 1.34. Found: C, 51.95; H,
1.74.
4
) 9.6 Hz, 2H), 7.40-7.43 (m, 2H) 7.26 (dt, J (H-F) ) 8.1 Hz,
3J (H-F) ) 9.9 Hz, 2H) ppm; 13C{1H, APT} NMR (100 MHz,
2
1
CDCl3): δ ) 151.8 (dt, J (C-F) ) 12.2 Hz, J (C-F) ) 248.3
Hz, 3,4-difluorophenyl), 147.6 (d br, 2J (C-F) ) 251.4 Hz, o- F5C6),
3
2
146.0 (d, J (C-P) ) 16.1 Hz, thiophene), 145.3 (d, J (C-F) )
X-ray Structure Determination. For compound 2, data were
collected on a Bruker SMART D8 goniometer with an APEX CCD
detector at 110 K, and for compound 4b on a Nonius KappaCCD
1
27.7 Hz, thiophene), 144.3 (d br, J (C-F) ) 258.4 Hz, p-F5C6),
137.9 (d br, J (C-F) ) 260.8 Hz, m-F5C6), 136.9 (d, 1J (C-P) )