View PDF Version
 
DOI: 10.1039/A904859F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 3877-3882

Platinum assisted cyclization of S-methyl 3-acyl-2-methyldithiocarbazates under mild conditions. Crystal structure of [Pt2(µ-SMe)(terpy)2][ClO4]3[hair space]†

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

Giuliano Annibale, Paola Bergamini, Valerio Bertolasi, Michela Cattabriga, Antonio Lazzaro, Andrea Marchi and Gianni Vertuani

Abstract

The reaction of the newly synthesized aqua complex [Pt(terpy)(OH2)][BF4]2 with S-methyl 3-acyl-2-methyldithiocarbazates under a variety of experimental conditions has been studied. Using a 2∶1 metal to ligand ratio in methanol, a platinum assisted cyclization was observed. The reaction products were Δ2-1,3,4-oxadiazoline-5-thione derivatives and the binuclear tricationic complex [Pt2(µ-SMe)(terpy)2]3+ whose molecular structure has been determined by X-ray crystallography. This platinum assisted transformation is proposed as a new synthetic route to Δ2-1,3,4-oxadiazoline-5-thiones under mild conditions. In the presence of an excess of a non-co-ordinating acid (HClO4, CH3SO3H or CF3SO3H) the cyclization is completely quenched and complexes with co-ordinated S-methyl 3-acyl-2-methyldithiocarbazates have been isolated. A general mechanism which accounts for the observed transformations is proposed on the basis of 1H NMR and UV/Vis evidence.

References

  1. A. Iakovidis and N. Hadjiliadis, Coord. Chem. Rev., 1994, 135/136, 17 CrossRef ; P. Bergamini, G. Fantin, M. Fogagnolo, L. Gualandi and A. Medici, Inorg. Chem. Commun., 1998, 1, 125 CrossRef CAS ; M. Stolmàr, C. Floriani, G. Gervasio and D. Viterbo, J. Chem. Soc., Dalton Trans., 1997, 1119 RSC .
  2. M. Cattabriga, A. Marchi, L. Marvelli, R. Rossi, G. Vertuani, R. Pecoraro, A. Scatturin, V. Bertolasi and V. Ferretti, J. Chem. Soc., Dalton Trans., 1998, 1453 RSC .
  3. M. Das and S. E. Livingstone, Inorg. Chim Acta, 1976, 19, 5 CrossRef CAS  and refs. therein A. Marchi, L. Uccelli, L. Marvelli, R. Rossi, M. Giganti, V. Bertolasi and V. Ferretti, J. Chem. Soc., Dalton Trans., 1996, 3105 Search PubMed .
  4. Metal Ions in Biological Systems, eds. A. Sigel and H. Sigel, Marcel Dekker, New York, 1996, vol. 32 Search PubMed .
  5. H. M. Brothers II and N. M. Kostic, Inorg. Chem., 1988, 27, 1761 CrossRef CAS ; H.-K. Yip, L.-K. Cheng, K.-K. Cheung and C.-M. Che, J. Chem. Soc., Dalton Trans., 1993, 2933 RSC ; B. Pitteri, C. Marangoni, L. Cattalini and T. Bobbo, J. Chem. Soc., Dalton Trans., 1995, 3853 RSC .
  6. S. J. Lippard, Acc. Chem. Res., 1978, 11, 211 CrossRef CAS .
  7. K. W. Jennette, J. T. Gill, J. A. Sadownick and S. J. Lippard, J. Am. Chem. Soc., 1976, 98, 6159 CrossRef CAS .
  8. (a) T. K. Aldrige, E. M. Stacey and D. R. McMillin, Inorg. Chem., 1994, 33, 722 CrossRef CAS ; (b) G. Annibale, L. Cattalini, F. Guidi, A. Cornia and A. Fabretti, Inorg. React. Mechanisms, in the press Search PubMed .
  9. (a) P. L. Goggin, R. J. Goodfellow and F. J. S. Reed, J. Chem. Soc. A, 1971, 2031 RSC ; (b) R. J. Puddephatt, K. A. Azam, R. H. Hill, M. P. Brown, C. D. Nelson, R. P. Moulding, K. R. Seddon and M. C. Grossel, J. Am. Chem. Soc., 1983, 105, 5642 CrossRef CAS ; (c) N. W. Alcock, P. Bergamini, T. J. Kemp, P. G. Pringle, S. Sostero and O. Traverso, Inorg. Chem., 1991, 30, 1594 CrossRef CAS .
  10. J. Hill, in Comprehensive Heterocyclic Chemistry, ed. K. T. Potts, Pergamon Press, Oxford, 1984, vol. 6, p. 427 Search PubMed .
  11. P. Molina, A. Tarraga and A. Espinosa, Synthesis, 1988, 690 CrossRef CAS .
  12. W. R. Sherman, J. Org. Chem., 1961, 26, 88 CrossRef CAS .
  13. F. Basolo and R. G. Pearson, in Mechanism of Inorganic Reactions, Wiley, New York, 2nd edn., 1968 Search PubMed ; L. Cattalini, Prog. Inorg. Chem., 1970, 13, 263 Search PubMed  and refs. therein.
  14. C. K. Johnson, ORTEP II, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976 .
  15. G. Marangoni, B. Pitteri, V. Bertolasi, V. Ferretti and P. Gilli, Polyhedron, 1996, 15, 2755 CrossRef CAS .
  16. C.-W. Chan, C.-M. Che, M.-C. Cheng and Y. Wang, Inorg. Chem., 1992, 31, 4874 CrossRef CAS .
  17. C.-W. Chan, T.-F. Lai, C.-M. Che and S.-M. Peng, J. Am. Chem. Soc., 1993, 115, 11245 CrossRef CAS .
  18. E. C. Constable, R. P. G. Henney, T. A. Leese and D. A. Tocher, J. Chem. Soc., Chem. Commun., 1990, 513 RSC .
  19. K. Umakoshi, I. Kinoshita, Y. Fukui-Yasuba, K. Matsumoto, S. Ooi, H. Nakai and M. Shiro, J. Chem. Soc., Dalton Trans., 1989, 815 RSC .
  20. D. Cruz-Garritz, E. Martin, H. Torrens, F. A. Mayoh and J. Smith, Acta Crystallogr., Sect. C, 1990, 46, 2377 CrossRef .
  21. Z. Bugarcic, B. Norén, Å. Oskarsson, C. Stålhandske and L. I. Elding, Acta Chem. Scand., 1991, 45, 361 CAS .
  22. M. I. Djuran, E. L. M. Lempers and J. Reedijk, Inorg. Chem., 1991, 30, 2648 CrossRef CAS ; A. K. Fazlur-Rahman and J. G. Verkade, Inorg. Chem., 1992, 31, 11 CrossRef .
  23. R. Usón, M. A. Usón, S. Herrero and L. Rello, Inorg. Chem., 1998, 37, 4473 CrossRef CAS .
  24. G. Annibale, M. Brandolisio and B. Pitteri, Polyhedron, 1995, 14, 451 CrossRef CAS .
  25. P. T. Beurskens, G. Beurskens, W. P. Bosnan, R. de Gelder, S. Garcia-Granda, R. O. Gould, R. Israel and J. M. M. Smits, DIRDIF, Crystallography Laboratory, University of Nijmegen, 1996 .
  26. G. M. Sheldrick, SHELXL 97, Program for the Renement of Crystal Structures, University of Göttingen, 1997 .
  27. M. Nardelli, J. Appl. Crystallogr., 1995, 28, 659 CrossRef CAS .
Click here to see how this site uses Cookies. View our privacy policy here.