P. Frꢀre, J. Roncali et al.
procedure by using 5b (0.94 mmol), 2,5-dibromothiophene (106 mg,
0.44 mmol), and [Pd(PPh3)4] (25 mg). The product was purified by chro-
matography on silica gel (CH2Cl2/EP 1/1, Et3N 1%) to give EETEE as a
red solid (70 mg, 20%).
EETEE: M.p. 2258C; 1H NMR (CDCl3): d=0.88 (t, 3J=6.8 Hz, 6H),
1.31 (m, 12H), 1.6 (m, 4H), 2.64 (t, 3J=7 Hz, 4H), 4.23 (m, 4H), 4.32
(m, 4H), 4.38 (s, 8H), 7.11 (s, 2H); Solubility was too low to measure the
13C NMR spectrum. HRMS calculated for C40H44O8S5: 812.16397; found:
812.1635.
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:5’’’,2’’’’ :5’’’’,2’’’’’,5’’’’’,2’’’’’’-septithiophene (TETETET): Stille coupling was
done according to the general procedure by using 4b (450 mg,
0.97 mmol), 3b (2.08 mmol), and [Pd(PPh3)4] (120 mg). The product was
purified by Soxhlet extraction with diethyl ether to remove impurities
and then acetone to obtain ETETETE as a red powder (120 mg, 14%).
The poor solubilty of the product prevented NMR spectroscopy. M.p.>
3008C; MS (MALDI-TOF) calculated for C46H46O6S7: 918.14; found:
918.00.
X ray structures: Data were collected at 293 K on an Enraf-Nonius
MACH3 four-circle diffractometer for ETTE and on a STOE-IPDS dif-
fractometer for TEET, both equipped with a graphite monochromator
utilizing MoKa radiation (l=0.71073 ꢃ). The structures were solved by
direct methods (SIR) and refined on F by full-matrix least-squares tech-
niques using MolEN package programs for ETTE and by full-matrix
least-squares methods on F2 with SHELXL97 for TEET.
Crystal data and structure refinement for ETTE: C16H19O2S2, Mr =307.43,
¯
yellow prism, 1.00ꢅ0.31ꢅ0.12 mm, triclinic, P1, a=12.316(1), b=
12.264(2), c=12.556(1) ꢃ, a=67.95(1), b=68.025(8), g=67.804(9)8, V=
1566.7(3) ꢃ3, Z=2, T=294 K, 1calcd =1.30 gcmꢀ3, 5795 reflections collect-
ed in the range q=2.5–25.08, 5519 independent reflections, of which 1490
with I>3s(I) converged to R=0.097 and wR2=0.131 with 201 parame-
ters, GOF=2.435. S and O atoms were refined anisotropically, and H
atoms were included in the calculation without refinement.
Crystal data and structure refinement for TEET: C16H19O2S2, Mr =307.43,
yellow plate, 0.46ꢅ0.40ꢅ0.03 mm, monoclinic, P21/n, a=12.835(2), b=
8.6701(8), c=15.097(2) ꢃ, b=113.67(2)8, V=1538.7(3) ꢃ3, Z=4, T=
293 K, 1calcd =1.327 gcmꢀ3, 11740 reflections collected in the range q=
1.8–25.88, 2868 independent reflections, of which 1400 with I>2s(I) con-
verged to R=0.054 and wR2=0.112 with 181 parameters, GOF=0.836.
All non-H atoms were refined anisotropically, and the H atoms were in-
cluded in the calculation without refinement. Absorption was corrected
by the multiscan technique.
CCDC-252647 and CCDC-252648 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of charge
c.uk/data_request/cif.
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Received: October 18, 2004
Revised: January 30, 2005
Published online: April 14, 2005
3752
ꢂ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2005, 11, 3742 – 3752