1,4-Dithiafulvene-substituted ferrocenes and their conversion into extended tetrathiafulvalene electron donors: synthetic, electrochemical and X-ray structural studies

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Adrian J. Moore, Martin R. Bryce, Peter J. Skabara, Andrei S. Batsanov, Leonid M. Goldenberg and Judith A. K. Howard


Abstract

The synthesis of 1,4-dithiafulvene-substituted ferrocene derivatives 7, 11 and 12 by reaction of formyl-, diformyl- and diacetyl-ferrocene, respectively, with the carbanion generated from reagents 4a–c and the ylide prepared from reagent 5 is reported. Upon reaction with HCl–diethyl ether, compounds 7a–c undergo an oxidative dimerisation to yield extended tetrathiafulvalene (TTF) derivatives 8a–c. The solution electrochemistry of compounds 7, 8, 11, 12, 14 and 16 has been studied by cyclic voltammetry. The X-ray crystal structures of compounds 8b and 12a are presented.


References

  1. T. K. Hansen and J. Becher, Adv. Mater., 1993, 5, 288 CrossRef CAS.
  2. Ferrocene, ed. A. Togni and T. Hayashi, VCH, Weinheim, Germany, 1995 Search PubMed.
  3. Reviews: (a) A. Krief, Tetrahedron, 1986, 42, 1209 CrossRef CAS; (b) G. Schukat and E. Fanghänel, Sulfur Rep., 1993, 14, 245 Search PubMed.
  4. Reviews: (a) M. R. Bryce, Chem. Soc. Rev., 1991, 20, 355 RSC; (b) A. E. Underhill, J. Mater. Chem., 1992, 2, 1 RSC.
  5. (a) Y. Misaki, T. Ohta, N. Higuchi, H. Fujiwara, T. Yamabe, T. Mori, H. Mori and S. Tanaka, J. Mater. Chem., 1995, 5, 1571 RSC; (b) Y. Yamashita, K. Ono, S. Tanaka, K. Imaeda and H. Inokuchi, Adv. Mater., 1994, 6, 295 CrossRef CAS; (c) M. R. Bryce, A. J. Moore, M. Hasan, G. J. Ashwell, A. T. Frazer, W. Clegg, M. B. Hursthouse and A. I. Karaulov, Angew. Chem., Int. Ed. Engl., 1990, 29, 1450 CrossRef.
  6. Review: M. R. Bryce and M. C. Petty, Nature (London), 1995, 374, 771 Search PubMed.
  7. (a) L. M. Goldenberg, R. Andreu, M. Savirón, A. J. Moore, J. Garín, M. R. Bryce and M. C. Petty, J. Mater. Chem., 1995, 5, 1593 RSC; (b) V. Morisson, C. Mingotaud, B. Agricole, M. Sallé, A. Gorgues, C. Garrigou-Lagrange and P. Delhaès, J. Mater. Chem., 1995, 5, 1617 RSC.
  8. (a) S. Frenzel, S. Arndt, R. M. Gregorious and K. Müllen, J. Mater. Chem., 1995, 5, 1529 RSC; (b) M. Fourmigué, I. Johannsen, K. Boubekeur, C. Nelson and P. Batail, J. Am. Chem. Soc., 1993, 115, 3752 CrossRef CAS; (c) H. Brisset, C. Thobiegautier, M. Jubault, A. Gorgues and J. Roncali, J. Chem. Soc., Chem. Commun., 1994, 1765 RSC.
  9. (a) T. Sugimoto, Y. Misaki, T. Kajita, Z. Yoshida, Y. Kai and N. Kasai, J. Am. Chem. Soc., 1987, 109, 4106 CrossRef CAS; (b) R. R. Schumaker, S. Rajeswari, M. V. Joshi, M. P. Cava, M. A. Takassi and R. M. Metzger, J. Am. Chem. Soc., 1989, 111, 308 CrossRef CAS.
  10. M. Jorgensen, K. Lerstrup, P. Frederiksen, T. Bjornholm, P. Sommerlarsen, K. Schaumberg, K. Branfeldt and K. Bechgaard, J. Org. Chem., 1993, 58, 2785 CrossRef.
  11. J.-M. Lehn, Angew. Chem., Int. Ed. Engl., 1990, 29, 1304 CrossRef.
  12. P. D. Beer, C. A. P. Dickson, N. Fletcher, A. J. Goulden, A. Grieve, J. Hodacora and T. Wear, J. Chem. Soc., Chem. Commun., 1993, 828 RSC.
  13. J. S. Miller and A. J. Epstein, Angew. Chem., Int. Ed. Engl., 1994, 33, 385 CrossRef.
  14. K. Akiba, K. Ishikawa and N. Inamoto, Bull. Chem. Soc. Jpn., 1978, 51, 2674 CAS.
  15. A. J. Moore and M. R. Bryce, J. Chem. Soc., Perkin Trans. 1, 1991, 157 RSC.
  16. (a) Preliminary communication: A. J. Moore, P. J. Skabara, M. R. Bryce, A. S. Batsanov, J. A. K. Howard and S. T. A. K. Daley, J. Chem. Soc., Chem. Commun., 1993, 417 Search PubMed; (b) for a subsequent report on related 1,4-dithiafulvenyl-substituted ferrocenes see: A. Togni, M. Hobi, G. Rihs, G. Rist, A. Albinati, P. Zanello, D. Zech and H. Keller, Organometallics, 1994, 13, 1224 Search PubMed.
  17. A. J. Moore and M. R. Bryce, Tetrahedron Lett., 1992, 33, 1373 CrossRef CAS.
  18. G. G. A. Balavoine, G. Doisneau and T. Fillebeen-Khan, J. Organomet. Chem., 1991, 412, 381 CrossRef CAS.
  19. N. C. Gonella and M. P. Cava, J. Org. Chem., 1979, 44, 930 CrossRef CAS.
  20. Y. Misaki, Y. Matsumura, T. Sugimoto and Z.-I. Yoshida, Tetrahedron Lett., 1989, 30, 5289 CrossRef CAS.
  21. For examples of acid mediated intramolecular cyclisations see: (a) A. S. Benhamed-Gasmi, P. Frère, A. Belyasmine, A. M. K. Malik, M. B. Hursthouse, A. J. Moore, M. R. Bryce, M. Jubault and A. Gorgues, Tetrahedron Lett., 1993, 34, 2131 CrossRef CAS; (b) P. Frère, A. Gorgues, M. Jubault, A. Riou, Y. Gouriou and J. Roncali, Tetrahedron Lett., 1994, 35, 1991 CrossRef CAS; (c) P. Leriche, A. Gorgues, M. Jubault, J. Becher, J. Orduna and J. Garín, Tetrahedron Lett., 1995, 36, 1275 CrossRef CAS For an example of acid mediated cis-trans isomerisation of substituted tetrathiafulvalene derivatives see: A. Souizi, A. Robert, P. Batail and L. Ouahab, J. Org. Chem., 1987, 52, 1610 Search PubMed.
  22. It is well known that TTF derivatives are oxidised to the radical cation in acid media. See for example: S. Hünig, G. Kiesslich, H. Quast and D. Scheutzow, Justus Liebigs Ann. Chem., 1973, 310 Search PubMed.
  23. V. Khodorkovsky(Ben-Gurion University of the Negev), personal communication. Calculations performed using Hyperchem 5.0.
  24. (a) W. Kirmse and L. Horner, Liebigs Ann. Chem., 1958, 614, 4 Search PubMed; (b) K. Mayer and H. Kröber, J. Prakt. Chem., 1974, 316, 907 CrossRef CAS; (c) M. P. Cava and M. V. Lakshmikantham, J. Heterocycl. Chem., 1980, 17, S39; (d) U. Schöberl, J. Salbeck and J. Daub, Adv. Mater., 1992, 4, 41 CrossRef; (e) A. Ohta and Y. Yamashita, J. Chem. Soc., Chem. Commun., 1995, 1761 RSC; (f) A. Benahmed-Gasmi, P. Frère, J. Roncali, E. Elandaloussi, J. Orduna, J. Garín, M. Jubault and A. Gorgues, Tetrahedron Lett., 1995, 36, 2983 CrossRef CAS; (g) A. Ohta and Y. Yamashita, Heterocycles, 1995, 40, 123 CAS; (h) A. Ohta and Y. Yamashita, Heterocycles, 1997, 44, 263.
  25. (a) D. Lorcy, R. Carlier, A. Robert, A. Tallec, P. Lemaguerès and L. Ouahab, J. Org. Chem., 1995, 60, 2443 CrossRef CAS; (b) P. Hapiot, D. Lorcy, A. Tallec, R. Carlier and A. Robert, J. Phys. Chem., 1996, 100, 14 823 CrossRef CAS.
  26. (a) M. Cais, Organomet. Chem. Rev., 1966, 1, 435 Search PubMed; (b) A. J. Deeming, in Comprehensive Organometallic Chemistry, ed. G. Wilkinson, F. G. A. Stone and E. W. Abel, Pergamon, Oxford, 1982 Search PubMed.
  27. M. Cais and A. Eisenstadt, J. Org. Chem., 1965, 1147.
  28. H. Hopf, M. Kreutzer and P. G. Jones, Angew. Chem., Int. Ed. Engl., 1991, 30, 1127 CrossRef.
  29. (a) A. J. Moore, M. R. Bryce, D. J. Ando and M. B. Hursthouse, J. Chem. Soc., Chem. Commun., 1991, 320 RSC; (b) M. R. Bryce, M. A. Coffin and W. Clegg, J. Org. Chem., 1992, 57, 1696 CrossRef CAS.
  30. M. A. Coffin, M. R. Bryce, A. S. Batsanov and J. A. K. Howard, J. Chem. Soc., Chem. Commun., 1993, 552 RSC.
  31. R. C. B. Copley, A. E. Goeta, C. W. Lehmann, J. C. Cole, D. S. Yufit and J. A. K. Howard, J. Appl. Crystallogr., 1997, 30, 413 CrossRef CAS.
  32. G. M. Sheldrick, SHELXTL-Plus, Structure Determination Software Programs, version 4.0, Siemens Analytical X-Ray Instruments Inc., Madison, Wisconsin, USA, 1990.
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