C O M M U N I C A T I O N S
Scheme 1. Synthesis of 1,3-Diaryl-4H-cyclopenta[c]thiophenes and Their Manganese Complexes
able to isolate η5-cyclopenta[c]thienyl products, even 3a that is
clearly stable.
(11) Bredas, J. L.; Themans, B.; Andre, J. M.; Heeger, A. J.; Wudl, F. Synth.
Met. 1985, 11, 343-352.
(12) Roncali, J. Chem. ReV. 1992, 92, 711-738.
In summary, 1,3-diaryl-4H-cyclopenta[c]thiophenes are effi-
ciently prepared from 1,2-diaroylcyclopentadienes by use of Lawes-
son’s reagent. η5-Cyclopenta[c]thienyl complexes, [Mn(η5-SC7H3-
1,3-R2)(CO)3] (3a,c; R ) Me, Ph), are prepared in high yield by
ligand substitution reactions of [MnBr(CO)5] with [SnMe3(SC7H3-
1,3-R2)]. Alternatively, thiation with P4S10/NaHCO3 converts [Mn-
{η5-1,2-C5H3(COR)2)(CO)3] (5c-e,h) to [Mn(η5-SC7H3-1,3-R2)-
(CO)3] (3c-e,h; R ) Ph, 4-tolyl, 4-MeOC6H4, benzo[2,3-b-]
thienyl).
(13) Roncali, J. Chem. ReV. 1997, 97, 173-205.
(14) Meng, H.; Wudl, F. Macromolecules 2001, 34, 1810-1816.
(15) Skramstad, J. Acta Chem. Scand. 1969, 23, 703-705.
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(17) Wallace, C. E. Ph.D. Dissertation, University of Kentucky, 1998.
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(21) Lloyd, D.; Preston, N. W. J. Chem. Soc. C 1969, 2464-2469.
(22) Mironov, V. A.; Fedorovich, A. D.; Yankovskii, S. A.; Luk’yanov, V.
T.; Kisin, A. V.; Akhrem, A. A. Dokl. Akad. Nauk SSSR 1976, 226, 592-
595.
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Acknowledgment. We thank the Research Corporation, the U.S.
Department of Energy (DE-FG02-00ER45847), and the University
of Kentucky Research Challenge Trust Fund for support.
1117.
(24) Jean, G. N.; Nord, F. F. J. Org. Chem. 1955, 20, 1363-1369.
(25) Jesberger, M.; Davis, T. P.; Barner, L. Synthesis 2003, 1929-1958.
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568.
Supporting Information Available: General procedures; syntheses
and spectroscopic data for 1d-h, 2c,f,g, 3a,c-e,h, 4a,b,d-h, and 5a-
h; tables of crystallographic details, atomic coordinates and displace-
ment parameters, bond distances, angles and crystallographic informa-
tion files (CIF) for the structures of 3a and 3c. This material is available
(27) Selected spectroscopic data: (3a) 1H NMR (200 MHz, C6D6, ppm) δ 4.66
3
3
(t, 1H, CHCHCH, JHH ) 2.6 Hz), 4.48 (d, 2H, CHCHCH, JHH ) 2.6
Hz), 2.07 (s, 3H, Me). 13C NMR (100 MHz, (CD3)2CO, ppm) δ 225.74
(b, CO), 123.20 (s, CH3CSC), 116.53 (s, CHCCS), 96.47 (dt, CHCHCH,
1JCH ) 176.07 Hz, 2JCH ) 5.89 Hz), 63.72 (dt, CHCHCH, 1JCH ) 182.71
Hz, JCH ) 5.89 Hz), 13.29 (q, Me, JCH ) 129.66 Hz). IR (KBr, cm-1
)
2
1
2011, 1917 (CO). (3c) 1H NMR (200 MHz, CDCl3, ppm) δ 5.47 (t, 3JHH
) 2.6 Hz, 1H, CHCHCH), 5.51 (d, 3JHH ) 2.6 Hz, 2H, CHCHCH), 7.28-
7.34 (m, 2H, Hpara), 7.41-7.48 (m, 4H, Hmeta), 7.67-7.70 (m, 4H, Hortho).
References
13C{1H} NMR (50 MHz, CDCl3, ppm)
δ 64.4 (CHCHCH), 96.6
(CHCHCH), 113.0, 125.5, 127.4, 128.9, 129.3, 133.7 (Ar), 224.0 (CO).
IR (KBr, cm-1) 2008, 1926 (CO), 1603 (CdC). See Supporting Informa-
tion for full data on all new compounds.
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(28) Selected crystallographic data: (3a) C12H9MnO3S, monoclinic, P21/m, a
) 6.4450(3) Å, b ) 9.0870(4) Å, c ) 9.9650(6) Å, b ) 96.7940(19)°, V
) 579.51(5) Å3, Z ) 2, θ ) 2.06 to 27.46°, 4030 reflections (1414 unique),
86 params, R1 ) 0.0320, wR2 ) 0.0716. (3c) C22H13MnO3S, triclinic,
P1h, a ) 11.1210(2) Å, b ) 13.2140(2) Å, c ) 13.3160(3) Å, R ) 66.5710-
(9)°, â ) 85.0370(9)°, γ ) 76.7720(9)°, V ) 1747.83(6) Å3, Z ) 4, θ )
1.67 to 25.00°, 12 168 reflections (6164 unique), 487 params, R1 ) 0.0552,
wR2 ) 0.1156. See Supporting Information for full details.
(29) Volz, H.; Kowarsch, H. Heterocycles 1977, 7, 1319-1337.
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Ser. Khim. 1979, 869-872.
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