p-Conjugated Dithienophospholes
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(d, J
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Acknowledgements
Ph), 123.3 (d, J
A
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MS (FAB): + VE 774.2 (100) [M+]; elemental analysis calcd (%) for
C50H35N2OPS2 (774.93): C 77.50, H 4.55 N 3.61; found: C 75.26, H 4.68 N
3.27.
The authors would like to thank Professor Jun Okuda for his generous
support of this work. Financial support of the Fonds der Chemischen In-
dustrie, BMBF, Deutsche Forschungsgemeinschaft (DFG) and from
OTKA (Grant No. T 049258) is gratefully acknowledged. We thank Dr.
K. Beckerle for the GPC analyses; T.B. thanks the University of Calgary
for start-up funding.
Synthesis of the polymer 8: To
a solution of phosphole 4 (0.55 g,
1.23 mmol) and fluorene(bisboronic) acid 7 (0.52 g, 1.23 mmol) in toluene
(20 mL) was added an aqueous solution of Na2CO3 (730 mg, 6.9 mmol, in
5 mL H2O). The emulsion was stirred vigorously, [Pd(PPh3)4] (71 mg,
G
0.06 mmol, 5 mol%) was added and the mixture was then refluxed for
20 h. During that time, the fluorescence of the solution changed from
green to orange and a bright orange solid precipitated from the reaction
mixture. The orange precipitate was filtered off, washed twice with water,
hot heptane and acetone, respectively, and evaporated to dryness under
vacuum to afford 8 as orange powder (594 mg; 78%). The reduced solu-
bility of the polymer precluded its comprehensive analysis. 1H NMR
(400 MHz, CD2Cl2): d=7.63 (brm, 13H; Ar), 1.94 (brs, 4H; 1-alkyl),
0.85 ppm (brm, 22H; CH3-/CH2-hexyl). GPC analysis (THF solution):
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M
W =3200 gmolꢀ1; Mn =2400 gmolꢀ1; PDI=1.37.
Synthesis of 9: To a solution of 6a (100 mg, 0.22 mmol) in CH2Cl2
.
(20 mL) an excess of BH3 SMe2 (2 mmol) was added at room temperature
and the reaction mixture was stirred for 1 h. Subsequently all volatile ma-
terials were removed under vacuum providing 9 as a yellow solid (89 mg,
95%). 31P{1H} NMR (80 MHz, CDCl3): d=14.9 ppm; 1H NMR
(400 MHz, CDCl3): d=7.71 (m, 2H; o-Ph), 7.69 (dd, 3J
4H), 7.59 (m, 4H), 7.49 (m, 1H, p-Ph), 7.41 (m, 8H), 7.32 (tt, 3J
Hz, 2H), 1.1 ppm (brs, 3H; BH3); 13C{1H} NMR (100 MHz, CDCl3): d=
148.3 (d, 2J
(C,P)=11.3 Hz; thiophene), 143.8 (s; phenyl), 141.1 (d,
2J(C,P)=12.1 Hz; thiophene), 139.7 (s; phenyl), 139.5 (d, 1J
(C,P)=
62.4 Hz; ipso-thiophene), 133.5 (s; phenyl), 132.1 (d, 1J
(C,P)=10.4 Hz;
ipso-Ph), 129.2 (s; phenyl), 129.1 (d, 4J
(C,P)=3.5 Hz; p-Ph), 128.3 (s;
(C,P)=15.6 Hz; m-Ph);
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phenyl), 125.7 (s; phenyl), 121.7 ppm (d, 3J
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11B{1H} NMR (128.4 MHz, CDCl3): d=ꢀ39.5 ppm.
Synthesis of 10: NEt3 (506 mg, 5 mmol) was added to a solution of com-
pound 9 (0.2 mmol) in CH2Cl2 at room temperature and stirred for 2 h.
After removing all volatile materials in vacuum the residue was taken up
in diethyl ether and filtered over neutral alumina. The filtrate was evapo-
rated to dryness and washed with pentane (72 mg, 85%). 31P{1H} NMR
(80 MHz, CDCl3): d=ꢀ22.2 ppm; 1H NMR (400 MHz, CDCl3): d=7.48
(m, 4H; o-Ar), 7.45 (m, 2H; o-Ph), 7.29 (s, 2H; thiophene), 7.28 (td, 4H;
p-Ar), 7.17 ppm (m, 5H); 13C{1H} NMR (100 MHz, CDCl3): d=146.6 (d,
1J
(d, J
ipso-Ph), 131.6 (d, 2J
128.5 (s; phenyl), 127.9 (s; phenyl), 127.7 (d, 3J
126.5 (s; phenyl), 124.5 (s; phenyl), 121.5 ppm (d, 2J
A
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G
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Ph); elemental analysis calcd (%) for C26H17PS2 (424.52): C 73.56, H
4.04; found: C 73.80, H 4.43.
Synthesis of 11: [Au(tht)Cl] (53 mg, 0.16 mmol) was added to a solution
E
of 10 (70 mg, 0.16 mmol) in CH2Cl2. After stirring 2 h at room tempera-
ture the solvent was removed in vacuum. The light yellow solid was fil-
tered with pentane through neutral alumina. Small yellow needles could
be obtained from a concentrated ether solution (99 mg, 95%). Crystals
of 11, suitable for X-ray analysis were obtained at room temperature
from a concentrated acetone solution. 31P{1H} NMR (80 MHz, CDCl3):
d=6.5 ppm; 1H NMR (400 MHz, CDCl3): d=7.65 (m, 2H; o-Ph), 7.54
(td 3J
(tt, 3J
CDCl3): d=147.5 (d, 2J
13.8 Hz; thiophene), 137.0 (d, 1J
(d, 1J(C,P)=15.6 Hz; ipso-Ph), 132.1 (s; phenyl), 131.7 (d, 4J
3.5 Hz; p-Ph), 128.5 (d, 2J
(C,P)=13.0 Hz; o-Ph), 128.4 (s; phenyl), 128.2
(s; phenyl), 127.5 (s; phenyl), 124.7 (s; phenyl), 120.5 ppm (d, 3J
(C,P)=
A
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[9] J. Roncali, Chem. Rev. 1997, 97, 173.
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[10] a) Phosphorus: The Carbon Copy (Eds.: K. Dillon, F. Mathey, J. F.
Nixon), Wiley, Chichester, 1998; b )Houben Weyl, Methods of Or-
ganic Chemistry, Vol. E1 & E2: Organic Phosphorus compounds I &
II (Ed.: M. Regitz), Thieme, Stuttgart, 1982; c) F. Mathey, A. Sevin,
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17.3 Hz; m-Ph); elemental analysis calcd (%) for C26H17AuClPS2·1/2
CH2Cl2 (699.41): C 45.07, H 2.55; found C 45.22, H 2.74.
Chem. Eur. J. 2007, 13, 7487 – 7500
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