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DOI: 10.1039/A705932I (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 623-628

Copper(I) complexes of dinucleating macrocyclic bis(dithiadiimine) ligands

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Gang Wei, Geoffrey A. Lawrance, David T. Richens, Trevor W. Hambley and Peter Turner

Abstract

The 34- and 36-membered macrocyclic bis(dithiadiimine) Schiff bases 3,17,26,40-tetrathia-6,14,29,37-tetraazapentacyclo[40.4.18,12.131,35.0.019,24]octatetraconta-6,8,10,12(47),13,19,21,23,29,31,33,35(48),36,42,44,46-hexadecaene (L3) and 3,16,25,38-tetrathia-6,13,28,35-tetraazapentacyclo[38.4.28,11.230,33.0.018,23]octatetraconta-6,8,10,12,18,20,22,28,30,32,34,40,42,44,45(46),47(48)-hexadecaene (L2) have been synthesized in high yield by a 2 + 2 condensation of isophthalaldehyde and terephthalaldehyde with 2,2′-o-phenylenebis(methylenethio)bis(ethanamine) (L1) in acetonitrile. Air-stable dicopper(I) complexes of L2 and L3 were obtained from complexation reactions with [Cu(CH3CN)4]ClO4 in CH3CN solution, with the structure of [Cu2L2][ClO4]2· 0.5CH3OH·2.5H2O confirmed by a crystal structure analysis. The complex consists of two N2S2 donor sets each tetrahedrally co-ordinated to the copper(I) ions with two para-substituted phenyl rings bridging the two N2S2 ‘compartments’ π-stacked parallel (separation 3.5 Å), and a double helical arrangement of the ligand backbone clearly evident. Electrochemical studies of the dinuclear complexes revealed quasi-reversible CuI–CuII couples above +1 V (versus NHE), with reversibility influenced by the presence of ferrocene, which acts as a surface modifier for electron transfer.

References

  1. E. C. Constable, Nature (London), 1990, 346, 314 CrossRef CAS.
  2. J.-P. Sauvage, Acc. Chem. Res., 1990, 23, 319 CrossRef CAS.
  3. J.-M. Lehn, Angew. Chem., Int. Ed. Engl., 1990, 29, 1304 CrossRef.
  4. E. C. Constable, Chem. Ind. (London), 1994, 56 CAS.
  5. K. D. Karlin and Z. Tyeklar(Editors), Bioinorganic Chemistry of Copper, Chapman and Hall, New York, London, 1993 Search PubMed.
  6. J. Reedijk(Editor), Bioinorganic Catalysis, Marcel Dekker, New York, 1993 Search PubMed.
  7. S. R. Cooper(Editor), Crown Compounds—Toward Future Applications, VCH, Weinheim, 1993 Search PubMed.
  8. P. A. Vigato, S. Tamburini and D. E. Fenton, Coord. Chem. Rev., 1990, 106, 25 CrossRef CAS.
  9. E. I. Solomon, M. J. Baldwin and M. D. Lowery, Chem. Rev., 1992, 92, 521 CrossRef CAS.
  10. T. N. Sorrell, Tetrahedron, 1989, 45, 3 CrossRef.
  11. U. Koert, M. M. Harding and J.-M. Lehn, Nature (London), 1990, 346, 339 CrossRef CAS.
  12. W. Zarges, J. Hall and J.-M. Lehn, Helv. Chim. Acta, 1991, 74, 1843 CrossRef.
  13. J. K. Judice, S. J. Keipert and D. J. Cram, J. Chem. Soc., Chem. Commun., 1993, 1323 RSC.
  14. R. Krämer, J.-M. Lehn, A. De Cian and J. Fischer, Angew. Chem., Int. Ed. Engl., 1993, 32, 703 CrossRef.
  15. E. C. Constable, A. J. Edwards, P. R. Raithby and J. V. Walker, Angew. Chem., Int. Ed. Engl., 1993, 32, 1465 CrossRef.
  16. A. Bilyk and M. M. Harding, J. Chem. Soc., Dalton Trans., 1994, 77 RSC.
  17. C. Piguet, G. Bernardinelli, B. Bocquet, A. Quattropani and A. F. Williams, J. Am. Chem. Soc., 1992, 114, 7440 CrossRef CAS.
  18. R. Ziessel and M.-T. Youinou, Angew. Chem., Int. Ed. Engl., 1993, 32, 877 CrossRef.
  19. D. E. Fenton, R. W. Matthews, M. McPartlin, B. P. Murphy, I. J. Scowen and P. A. Tasker, J. Chem. Soc., Chem. Commun., 1994, 1391 RSC.
  20. T. Adatia, N. Beynek and B. P. Murphy, Polyhedron, 1995, 14, 335 CrossRef CAS.
  21. S. M. Nelson, Pure Appl. Chem., 1980, 52, 2461 CrossRef CAS; D. E. Fenton, Pure Appl. Chem., 1986, 58, 1437 CrossRef CAS.
  22. S. R. Cooper, in Crown Compounds Toward Future Applications, ed. S. R. Cooper, VCH, Weinheim, 1992, p. 112 Search PubMed.
  23. R. Menif and A. E. Martell, J. Chem. Soc., Chem. Commun., 1989, 1521 RSC.
  24. D. E. Fenton, S. J. Kitchen, C. M. Spencer, S. Tamburini and R. Vigato, J. Chem. Soc., Dalton Trans., 1988, 685 RSC.
  25. S. Brooker, V. McKee, W. B. Shepard and L. K. Pannell, J. Chem. Soc., Dalton Trans., 1987, 2555 RSC.
  26. M. G. B. Drew, D. McDowell and J. Nelson, Polyhedron, 1988, 7, 2229 CrossRef CAS.
  27. M. G. B. Drew, D. Marrs, J. Hunter and J. Nelson, J. Chem. Soc., Dalton Trans., 1992, 11 RSC.
  28. M. P. Ngwenya, A. E. Martell and J. Reibenspies, J. Chem. Soc., Chem. Commun., 1990, 1207 RSC.
  29. G. Morgan, V. McKee and J. Nelson, Inorg. Chem., 1994, 33, 4427 CrossRef CAS.
  30. P. Comba, A. Fath, T. W. Hambley and D. T. Richens, Angew. Chem., Int. Ed. Engl., 1995, 34, 1883 CrossRef CAS.
  31. TEXSAN, Crystal Structure Analysis Package, Molecular Structure Corporation, The Woodlands, TX, 1985 and 1992.
  32. A. Altomare, M. Cascarano, C. Giacovazzo and A. Guagliardi, J. Appl. Crystallogr., 1993, 26, 343 CrossRef.
  33. P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, R. de Gelder, R. Israel and J. M. M. Smits, DIRDIF 94, Technical Report of the Crystallography Laboratory, University of Nijmegen, 1994.
  34. A. J. Elliott, G. A. Lawrance and G. Wei, Polyhedron, 1993, 12, 851 CrossRef CAS.
  35. J. van Rijn and J. Reedijk, J. Chem. Soc., Dalton Trans., 1987, 2579 RSC.
  36. M. J. Eddowes and H. A. O. Hill, J. Am. Chem. Soc., 1979, 101, 4461 CrossRef CAS.
  37. F. A. Armstrong, H. A. O. Hill and N. J. Walton, Acc. Chem. Res., 1988, 21, 407 CrossRef CAS.
  38. P. Comba, personal communication.
  39. C. K. Johnson, ORTEP, A Thermal Ellipsoid Plotting Program, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
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