Skip to main content
SpringerLink
Log in

Ein Beitrag zum Tetrathiaporphycen-Redoxsystem: Elektrochemische Reduktion eines 20π-Cyclophans zum diatropen 22π-Dianion

The tetrathiaporphycene redox system: Electrochemical reduction of a 20π cyclophane to its diatropic 22π dianion

  • Organische Chemie Und Biochemie
  • Published:
Monatshefte für Chemie / Chemical Monthly Aims and scope Submit manuscript

Summary

The reductive carbonyl coupling (McMurry reaction) of 5,5′-diformyl-2,2′-bithiophene affords the fourfold sulfur bridged [20]annulene5 and its [30]annulene homologue10 in 8 and 3% yields. Coupling of 5,5″-diformyl-2,2′:5′,2″-terthiophene produces structurally related macrocycles, albeit in very low yields. As shown by X-ray crystallographic investigation, the bridged annulenes5 and10 are non-planar cyclophanes exhibiting transannular electronic interaction. The sulfur bridged [20] annulene5 constitutes the central molecule of the tetrathiaporphycene redox system emcompassing the dicationic tetrathiaporphycene3, the annulene5, the 22π dianion8 and the two intermediate radical ion species. Compound5 is reduced in one two-electron step giving the diatropic 22-π dianion8 which is characterized by cyclovoltammetry, coulometry, spectroelectrochemistry and1H-NMR spectroscopy. By contrast,5 fails to undergo oxidation with formation of the dicationic 18π tetrathioporphycene.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

Literatur

  1. Vogel E., Köcher M., Schmickler H., Lex J. (1986) Angew. Chem.98: 262

    Google Scholar 

  2. Vogel E., Hass W., Knipp B., Lex J., Schmickler H. (1988) Angew. Chem.100: 445;

    Google Scholar 

  3. Hass W., Knipp B., Sicken M., Lex J., Vogel E. (1988) Angew. Chem.100: 448

    Google Scholar 

  4. Vogel E., Sicken M., Röhrig P., Schmickler H., Lex J., Ermer O. (1988) Angew. Chem.100: 450

    Google Scholar 

  5. Knübel G., Franck B. (1988) Angew. Chem.100: 450

    Google Scholar 

  6. Sessler J. I., Takashi M., Lynch V. (1991) Angew. Chem.103: 1018

    Google Scholar 

  7. Vogel E., Röhrig P., Sicken M., Knipp B., Herrmann B., Pohl M., Schmickler H., Lex J. (1989) Angew. Chem.101: 1683

    Google Scholar 

  8. Vogel E., Grigat I., Köcher M., Lex J. (1989) Angew. Chem.101: 1687

    Google Scholar 

  9. 5 und10 wurden unabhängig in den Arbeitsgruppen Merz A. (Regensburg), Neidlein R. (Heidelberg) und Vogel E. (Köln) synthetisiert

  10. Ankner K., Lamm B., Thulin B., Wennerström O. (1980) J. Chem. Soc., Perkin Trans.2: 1301

    Google Scholar 

  11. McMurry J. E. (1983) Acc. Chem. Res.16: 405 (vgl. [7])

    Google Scholar 

  12. Geise H. J., Westrop I., Dams R., Malinowski M. (1982) J. Org. Chem.47: 248

    Google Scholar 

  13. Hoffman R. V., Orphanides G. G., Shechter H. (1978) J. Amer. Chem. Soc.100: 7927

    Google Scholar 

  14. Die Kristallstrukturanalyse von5 wurde unabhängig sowohl von Neidlein R., Lucchesini F., Gieren A. und Hübner T. als auch von Vogel E. und Lex J. ausgeführt

  15. Neidlein R., Lucchesini F., Gieren A., Hübner T. (1987) Jahrbuch der Max-Planck-Gesellschaft:144; (1989) Chem. Abstr.110: 951129q

  16. Cram D. J. (1983) In: Keehn P. M., Rosenfeld S. M. (eds.) Cyclophanes. Academic Press, New York, p. 8

    Google Scholar 

  17. Tourillon G., Garnier F. (1982) J. Electroanal. Chem.135: 173; Skotheim (Hrsg) (1986) Handbook of Conducting Polymers. Marcel Dekker, New York

    Google Scholar 

  18. Hinkelmann K., Heinze J. (1987) Ber. Bunsenges. Phys. Chem.91: 243

    Google Scholar 

  19. Myers R. L., Shain I. (1969) Anal. Chem.41: 980; Richardson D. E., Taube H. (1981) Inorg. Chem.127: 1728

    Google Scholar 

  20. Rieke R. D., Copenhafer R. A. (1974) J. Electroanal. Chem.56: 409; siehe auch: Fry A. J., Hutchins C. S., Ling L. C. (1975) J. Am. Chem. Soc.97: 591; Jensen B. S., Ronlan A., Parker V. D. (1975) Acta Chem. Scand.B29: 394; andere Ursachen für invertierte Potentiale siehe Salbeck J., Schöberl U., Rapp K. M., Daub J. (1991) Z. Phys. Chem.171: 191

    Google Scholar 

  21. Bard A. J., Faulkner L. L. (1980) In: Electrochemical Methods. Wiley, New York, S. 406

    Google Scholar 

  22. Rao C. N. R., Kalyanaraman V., George V. M. (1970) Appl. Spec. Rev.3: 153

    Google Scholar 

  23. Müllen K., Unterberg H., Huber W., Wennerström O., Norinder U., Tanner D., Thulin B. (1984) J. Am. Chem. Soc.106: 7514

    Google Scholar 

  24. Das diatrope7 wurde kürzlich nachgewiesen: Vogel E. (1992) persönliche Mitteilung

  25. Fry A. J., Britton W. E. (1984) In: Kissinger P. T., Heinemann W. R. (Hrsg.) Laboratory Techniques in Electroanalytical Chemistry. Marcel Dekker, New York, S. 378

    Google Scholar 

  26. Fujinaga T., Izutsu K., Skura S. (1983) In: Coetze J. F. (Hrsg.) Recommended Methods for Purification of Solvents and Tests for Impurities. Pergamon Press, Oxford, S. 10

    Google Scholar 

  27. Carlier R., Simonet J. (1988) Bull. Soc. Chim. Fr.: 831

  28. Salbeck J., Aurbach I., Daub J. (1988) In: Russow J. (Hrsg.) Dechema-Monographie Bd. 112. VCH, Weinheim, S. 177; Salbeck J. (im Druck) Anal. Chem.

    Google Scholar 

  29. Koßmehl D., Budwill R. (1986) Z. Naturforsch.41B: 751

    Google Scholar 

  30. McEachern A., Soucy C., Leitch L. C., Arnason J. T., Morand P. (1988) Tetrahedron44: 2403

    Google Scholar 

  31. Vögtle F., Neumann P. (1970) Tetrahedron26: 5847

    Google Scholar 

Download references

Author information

Author notes

  1. A. Gieren

    Present address: Institut für Anorganische und Analytische Chemie, Universität Innsbruck, Innrain 52a, A-6020, Innsbruck, Österreich

  2. F. Lucchesini

    Present address: Dipartamento di Chimica, Universitát della Calabria, I-87030, Arcavacata di Rende, Italia

Authors and Affiliations

  1. Institut für Organische Chemie, Universität Regensburg, D-8400, Regensburg, Bundesrepublik Deutschland

    F. Ellinger, A. Merz & J. Salbeck

  2. Max-Plank-Institut für Biochemie, D-8033, Martinsried, Bundesrepublik Deutschland

    A. Gieren & Th. Hübner

  3. Institut für Organische Chemie, Universität Köln, D-5000, Köln, Bundesrepublik Deutschland

    J. Lex

  4. Pharmazeutisch-Chemisches Institut, Universität Heidelberg, D-6900, Heidelberg, Bundesrepublik Deutschland

    F. Lucchesini & R. Neidlein

Authors
  1. F. Ellinger
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. Gieren
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Th. Hübner
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. J. Lex
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. F. Lucchesini
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. A. Merz
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. R. Neidlein
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. J. Salbeck
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Ellinger, F., Gieren, A., Hübner, T. et al. Ein Beitrag zum Tetrathiaporphycen-Redoxsystem: Elektrochemische Reduktion eines 20π-Cyclophans zum diatropen 22π-Dianion. Monatsh Chem 124, 931–943 (1993). https://doi.org/10.1007/BF00816416

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00816416

Keywords

Search

Navigation