View PDF Version
 
DOI: 10.1039/A700711F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 2409-2418

Copper complexes of 1,3-bis(2-pyridyl)-1-thiapropane (bpt) and pyridine-2(1H)-thione. Crystal structure of [{Cu(µ-O2CMe)2(bpt)}2 ] and metal-promoted cleavage of bpt

(Note: The full text of this document is currently only available in the PDF Version )

Sian C. Davies, Marcus C. Durrant, David L. Hughes, Kerstin Leidenberger, Christian Stapper and Raymond L. Richards

Abstract

The reactivity of the asymmetric thioether 1,3-bis(2-pyridyl)-1-thiapropane [1-(2-pyridyl)-2-(2-pyridylsulfanyl)ethane] (bpt) with copper-(I) and -(II) starting materials has been investigated. Reaction with [Cu(NCMe)4]PF6 in MeCN gave a cluster formulated as [Cu4(bpt)6][PF6]4, whilst reaction in tetrahydrofuran resulted in partial cleavage of bpt to give the mixed thionato–thioether complex [Cu2(SC5H4N)(bpt)]PF6 [SC5H4NH = pyridine-2(1H)- thione]. Reaction with [Cu2(µ-O2CMe)4] in MeOH gave the dimer [{Cu(µ-O2CMe)2(bpt)}2 ], whose crystal structure shows that the bpt ligands are monodentate and co-ordinated via the N atom remote from the thioether. The compound bpt undergoes cleavage with other copper(II) salts such as Cu(BF4)2, ultimately giving the hexameric copper(I) complex [Cu6(SC5H4N)6]. The details of this reaction have been investigated. Reaction of SC5H4NH with Cu(NO3)2 in the presence of HNO3 gave [Cu(NO3)(SC5H4NH)2], which in turn reacted progressively with PPh3 to give [Cu(NO3)(SC5H4NH)2(PPh 3)] and the known complex [Cu(SC5H4NH)2(PPh3)2 ]NO3, whose crystal structure has been determined. Other complexes of SC5H4NH with copper(I) and a range of anions have been prepared, and the crystal structure of the dimer [Cu2(SC5H4NH)6][MeC6 H4SO3]2 is reported.

References

  1. A. Messerschmidt, Adv. Inorg. Chem., 1993, 40, 121.
  2. A. G. Sykes, Struct. Bonding (Berlin), 1991, 75, 175 CAS.
  3. J. W. Godden, S. Turley, D. C. Teller, E. T. Adman, M. Y. Liu, W. J. Payne and J. LeGall, Science, 1991, 253, 438 CAS.
  4. W. Kaim and J. Rall, Angew. Chem., Int. Ed. Engl., 1996, 35, 43 CrossRef CAS.
  5. J. Gazo, I. B. Bersuker, J. Garaj, M. Kabesova, J. Kohout, H. Langfelderova, M. Melník, M. Serator and F. Valach, Coord. Chem. Rev., 1976, 19, 253 CrossRef CAS.
  6. E. Bouwman, W. L. Driessen and J. Reedijk, Coord Chem. Rev., 1990, 104, 143 CrossRef CAS.
  7. M. C. Durrant, C. Hauser, D. L. Hughes, M. J. Maguire and R. L. Richards, J. Organomet. Chem., 1994, 476, 219 CrossRef CAS.
  8. M. Melník, Coord. Chem. Rev., 1982, 42, 259 CrossRef CAS.
  9. G. A. Barclay and C. H. L. Kennard, J. Chem. Soc., 1961, 5244 RSC.
  10. M. Melník, K. Smolander and P. Sharrock, Inorg. Chim. Acta, 1985, 103, 187 CrossRef CAS.
  11. S. Emori, K. Ohishi, H. Kurihara and Y. Muto, Bull. Chem. Soc. Jpn., 1988, 61, 4439 CAS.
  12. W. J. Geary, Coord. Chem. Rev., 1971, 7, 81 CrossRef CAS.
  13. S. Kitagawa, M. Munakata, H. Shimono, S. Matsuyama and H. Masuda, J. Chem. Soc., Dalton Trans., 1990, 2105 RSC.
  14. A. J. Blake, A. J. Holder, T. I. Hyde, H. J. Küppers, M. Schröder, S. Stötzel and K. Wieghardt, J. Chem. Soc., Chem. Commun., 1989, 1600 RSC.
  15. E. S. Raper, Coord. Chem. Rev., 1994, 129, 91 CrossRef CAS.
  16. W. Marckwald, W. Klemm and H. Trabert, Ber. Dtsch. Chem. Ges., 1900, 33, 1556.
  17. I. P. Evans and G. Wilkinson, J. Chem. Soc., Dalton Trans., 1974, 946 RSC.
  18. N. Lenhart and H. Singer, Z. Naturforsch., Teil B, 1975, 30, 284 Search PubMed.
  19. E. C. Constable and P. R. Raithby, J. Chem. Soc., Dalton Trans., 1987, 2281 RSC.
  20. G. A. Stergioudis, S. C. Kokkou, P. J. Rentzeperis and P. Karagiannidis, Acta Crystallogr., Sect. C, 1987, 43, 1685 CrossRef.
  21. S. C. Kokkou, S. Fortier, P. J. Rentzeperis and P. Karagiannidis, Acta Crystallogr., Sect. C, 1983, 39, 178 CrossRef.
  22. P. Karagiannidis, P. Aslanidis, P. Papastefanou, D. Mentzafos, A. Hountas and A. Terzis, Inorg. Chim. Acta, 1989, 156, 265 CrossRef.
  23. P. Karagiannidis, P. Aslanidis, S. Papastefanou, D. Mentzafos, A. Hountas and A. Terzis, Polyhedron, 1990, 9, 2833 CrossRef CAS.
  24. I. G. Dance, G. A. Bowmaker, G. R. Clark and J. K. Seadon, Polyhedron, 1983, 2, 1031 CrossRef CAS; G. Henkel, B. Krebs, P. Betz, H. Fietz and K. Saatkamp, Angew. Chem., Int. Ed. Engl., 1988, 27, 1326 CrossRef.
  25. A. L. E. Stoffels, W. G. Haanstra, W. L. Driessen and J. Reedijk, Angew. Chem., Int. Ed. Engl., 1990, 29, 1419 CrossRef.
  26. E. W. Ainscough, A. M. Brodie, J. M. Husbands, G. J. Gainsford, E. J. Gabe and N. F. Curtis, J. Chem. Soc., Dalton Trans., 1985, 151 RSC.
  27. K. Nilsson and Å. Oskarsson, Acta Chem. Scand., Ser. A, 1982, 36, 605.
  28. S. Ahrland, S. Ishiguro and I. Persson, Acta Chem. Scand., Ser. A, 1986, 40, 418.
  29. D. S. Gill, L. Rodehüser and J.-J. Delpuech, J. Chem. Soc., Faraday Trans., 1990, 2847 RSC.
  30. C. J. Pouchert and J. Behnke, The Aldrich Library of 13C and 1H FT NMR Spectra, 1st edn., Adrich Chemical Company Inc., Milwaukee, 1993 Search PubMed.
  31. A. Albert and G. B. Barlin, J. Chem. Soc., 1959, 2384 RSC.
  32. S. Stoyanov, I. Petkov, L. Antonov, T. Stoyanova, P. Karagiannidis and P. Aslanidis, Can. J. Chem., 1990, 68, 1482 CAS and refs. therein.
  33. M. J. Nowak, L. Lapinski, H. Rostkowska, A. Les and L. Adamowicz, J. Phys. Chem., 1990, 94, 7406 CrossRef CAS.
  34. J. S. Kwiatkowsi, J. Mol. Struct., 1971, 10, 245 CrossRef.
  35. L. Stefaniak, Org. Magn. Reson., 1979, 12, 379 Search PubMed.
  36. L. Stefaniak, G. A. Webb, C. Brevard, M. Bourdonneau, R. Lejeune, L. Thunus and C. L. Lapière, Magn. Reson. Chem., 1985, 23, 790 CAS.
  37. J. Mason, in Encyclopedia of Nuclear Magnetic Resonance, eds. D. M. Grant and R. K. Harris, Wiley, Chichester, 1996, pp. 3222–3251 Search PubMed.
  38. D. F. Shriver, Inorg. Synth., 1979, 19, 90 CAS.
  39. D. F. Evans and T. A. James, J. Chem. Soc., Dalton Trans., 1979, 723 RSC; M. V. Baker, L. D. Field and T. W. Hambley, Inorg. Chem., 1988, 27, 2872 CrossRef CAS.
  40. G. M. Sheldrick, SHELX 76, Program for Crystal Structure Determination, University of Cambridge, 1976; also SHELXN, an extended version of SHELX 76, 1977.
  41. International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4, pp. 99 and 149 Search PubMed.
  42. S. N. Anderson, R. L. Richards and D. L. Hughes, J. Chem. Soc., Dalton Trans., 1986, 245 RSC.
  43. G. M. Sheldrick, Acta Crystallogr., Sect. A, 1990, 46, 467 CrossRef.
Click here to see how this site uses Cookies. View our privacy policy here.