The reaction of N-methylbenzothiazole-2-selone and 1,1-dimethylselenourea with sulfuryl chloride and dichlorine †

Abstract

The reactions of N-methylbenzothiazole-2-selone, mbts, and 1,1-dimethylselenourea, dmsu, with dichlorine and the chlorinating agent SO₂Cl₂ have been investigated. In the 1∶1 reactions spectroscopic evidence for the formation of 1∶1 selenoamide·Cl₂ adducts was obtained; unfortunately, crystallisation attempts have so far been unsuccessful. A single crystal X-ray diffraction was performed, however, on an ionic minor product from the reaction of mbts with one equivalent of SO₂Cl₂. When two equivalents of SO₂Cl₂ or an excess of dichlorine gas were treated with mbts or dmsu a variety of ionic products were obtained, the exact nature of which varied depending upon which chlorinating agent is used, the identity of the selenoamide and the stoichiometry of the reactants. The reactions are therefore complicated and, in most cases, several products are obtained from a given reaction. This study represents the first reported reactions of selenoamides with chlorinating agents and two new selenium–chlorine binary anions have been crystallographically characterised for the first time, namely Se₂Cl₄^2– and SeCl₆^2–.

References

1. C. A. McAuliffe, B. Beagley, G. A. Gott, A. G. Mackie, P. P. MacRory and R. G. Pritchard, Angew. Chem., Int. Ed. Engl., 1987, 26, 264.
2. N. Bricklebank, S. M. Godfrey, H. P. Lane, C. A. McAuliffe, R. G. Pritchard and J.-M. Morens, J. Chem. Soc., Dalton Trans., 1995, 3873.
3. S. M. Godfrey, D. G. Kelly, C. A. McAuliffe, A. G. Mackie, R. G. Pritchard and S. M. Watson, J. Chem. Soc., Chem. Commun., 1991, 1163.
4. S. M. Godfrey, S. L. Jackson, C. A. McAuliffe and R. G. Pritchard, J. Chem. Soc., Dalton Trans., 1997, 4499.
5. S. M. Godfrey, S. L. Jackson, C. A. McAuliffe and R. G. Pritchard, J. Chem. Soc., Dalton Trans., 1998, 4201.
6. F. Cristiani, F. Demartin, F. A. Devillanova, F. Isaia, V. Lippolis and G. Verani, Inorg. Chem., 1994, 33, 6315; F. Demartin, P. Deplano, F. A. Devillanova, F. Isaia, V. Lippolis and G. Verani, Inorg. Chem., 1993, 32, 3694; F. Bigoli, A. M. Pellinghelli, P. Deplano, F. A. Devillanova, V. Lippolis, M. L. Mercuri and E. F. Trogu, Gazz. Chim. Ital., 1994, 124, 445.
7. P. D. Boyle, W. I. Cross, S. M. Godfrey, C. A. McAuliffe, R. G. Pritchard and S. J. Teat, J. Chem. Soc., Dalton Trans., 1999, 2219.
8. P. D. Boyle, W. I. Cross, S. M. Godfrey, C. A. McAuliffe, R. G. Pritchard and S. J. Teat, J. Chem. Soc., Dalton Trans., 1999, 2845.
9. F. A. Devillanova, P. Deplano, F. Isaia, V. Lippolis, M. L. Mercuri, S. Piludu, G. Verani and F. Demartin, Polyhedron, 1998, 17, 305.
10. D. J. Williams, D. Vanderveer, B. R. Crouse, R. R. Raye, T. Carter, K. S. Hagen and M. Brewer, Main Group Chem., 1997, 2, 61.
11. J. D. McCullough and G. Hamburger, J. Am. Chem. Soc., 1942, 64, 508.
12. J. D. McCullough and R. E. Marsh, Acta Crystallogr., 1950, 3, 41.
13. D. G. Garratt, P.-T. Cheng, S. C. Nyburg and G. H. Schmid, Cryst. Struct. Commun., 1974, 3, 361.
14. A. Amendola, E. S. Gould and B. Post, Inorg. Chem., 1964, 3, 1199.
15. S. M. Godfrey, C. A. McAuliffe, R. G. Pritchard and S. Sarwar, J. Chem. Soc., Dalton Trans., 1997, 1031.
16. K. J. Wynne and J. W. George, J. Am. Chem. Soc., 1965, 87, 4750.
17. S. Akabori, Y. Takanohashi, S. Aoki and S. Sato, J. Chem. Soc., Perkin Trans. 1, 1991, 3121.
18. F. Wudl and E. T. Zellers, J. Am. Chem. Soc., 1980, 102, 5430.
19. C. K. Johnson, ORTEP II, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
20. E. G. Awere, N. Burford, R. C. Haddon, S. Parsons, J. Passmore, J. V. Waszczak and P. S. White, Inorg. Chem., 1990, 29, 4821.
21. T. Chivers, J. F. Richardson and N. R. M. Smith, Inorg. Chem., 1985, 24, 2453.
22. A. Aharoni, M. Kapon and G. M. Reisner, Acta Crystallogr., Sect. C, 1989, 45, 40.
23. E. B. Chuklanova, A. I. Gusev, A. S. Zhdanov, Z. V. Belyakova, V. M. Shevchenko and V. D. Sheludya, Koord. Khim., 1987, 13, 1109.
24. S. Husebye, S. V. Lindeman and M. D. Rudd, Acta Crystallogr., Sect. C, 1997, 53, 809.
25. B. Neumuller, C. Lau and K. Dehnicke, Z. Anorg. Allg. Chem., 1996, 622, 1847.
26. B. Krebs, E. Lührs, R. Willmer and F.-P. Ahlers, Z. Anorg. Allg. Chem., 1991, 592, 17.
27. R. J. Gillespie, J. P. Kent and J. F. Sawyer, Inorg. Chem., 1990, 29, 1251.
28. H. Folkerts, K. Dehnicke, J. Magull, H. Goesmann and D. Fenske, Z. Anorg. Allg. Chem., 1994, 620, 1301.
29. C. J. Carmalt, L. J. Farrugia and N. C. Norman, Polyhedron, 1995, 14, 1405.
30. B. Krebs, N. Rieskamp and A. Schäffer, Z. Anorg. Allg. Chem., 1986, 532, 118.
31. A. J. Privett, S. L. Craig, D. Y. Jeter, A. W. Cordes, R. T. Oakley and R. W. Reed, Acta Crystallogr., Sect. C, 1987, 43, 2023.
32. G. M. Sheldrick, SHELX 97, Programs for crystal structure analysis (release 97-2), University of Göttingen, 1998.