View PDF Version
 
DOI: 10.1039/A705886A (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 4747-4752

Disproportionation and reduction of hydrazine at a molybdenum–thiolate centre: crystal structures of [MoH(SC6H2Pri3-2,4,6)3(NH3)(PMePh2)] and [MoH(SC6H2Pri3-2,4,6)3(NH2NHPh)(PMePh2)]

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

Peter B. Hitchcock, David L. Hughes, Michael J. Maguire, Katayoun Marjani and Raymond L. Richards

Abstract

In the presence of [MoH(SC6H2Pri3-2,4,6)3(PMePh2)] in tetrahydrofuran (thf[hair space]), anhydrous N2H4 disproportionates to N2 and NH3 or is reduced to NH3 by Zn–HOC6H3Pri2-2,6 (69–81% conversion over 16 h). Reaction of [MoH(SC6H2Pri3-2,4,6)3(PMePh2)] with anhydrous N2H4 in thf–MeOH at low temperature gave the complex [MoH(SC6H2Pri3-2,4,6)3(NH3)(PMePh2)] which was shown by a crystal-structure determination to have a trigonal girdle of thiolate ligands with essentially apical NH3 and PMePh2 ligands [d(Mo–N), 2.298(15); d(Mo–S) (mean), 2.339(5) Å]. A similar reaction using NH2NHPh instead of N2H4 gave [MoH(SC6H2Pri3-2,4,6)3(NH2NHPh)(PMePh2)], which has an analogous crystal structure to [MoH(SC6H2Pri3-2,4,6)3(NH3)(PMePh2)] [d(Mo–N), 2.278(5); d(Mo–S) (mean), 2.332(2); d(N–N) 1.451(7) Å]. Spectroscopic data for these compounds are discussed in terms of their structures. The unstable adduct [MoH(SC6H2Pri3-2,4,6)3(NH2NMe2)(PMePh2)] has been characterised spectroscopically in solution.

References

  1. R. R. Schrock, T. E. Glassman, M. G. Vale and M. Kol, J. Am. Chem. Soc., 1993, 115, 725.
  2. K. D. Demadis, S. M. Malinak and D. Coucouvanis, Inorg. Chem., 1996, 35, 4038 CrossRef CAS and refs. therein.
  3. D. Coucouvanis, P. E. Mosier, K. D. Demadis, S. Patton, S. M. Malinak, C. G. Kim and M. A. Tyson, J. Am. Chem. Soc., 1993, 115, 12 193 CrossRef CAS.
  4. R. L. Richards, Coord. Chem. Rev., 1996, 154, 83 CrossRef CAS and refs. therein.
  5. E. Block, G. Ofori-Okai, H. Kang and J. Zubieta, J. Am. Chem. Soc., 1992, 114, 758 CrossRef CAS.
  6. P. Schollhammer, F. Y. Petillon, S. Poder-Guillou, J. Y. Saillard, J. Talarmin and K. W. Muir, Chem. Commun., 1996, 2633 RSC.
  7. D. L. Hughes, N. J. Lazarowych, M. J. Maguire, R. H. Morris and R. L. Richards, J. Chem. Soc., Dalton Trans., 1995, 5 RSC.
  8. T. E. Burrow, D. L. Hughes, A. J. Lough, M. J. Maguire, R. H. Morris and R. L. Richards, J. Chem. Soc., Dalton Trans., 1995, 1315 RSC.
  9. T. E. Burrow, A. Hills, D. L. Hughes, J. D. Lane, N. J. Lazarowych, M. J. Maguire, R. H. Morris and R. L. Richards, J. Chem. Soc., Dalton Trans., 1991, 2519 RSC.
  10. R. N. F. Thorneley, R. R. Eady and D. J. Lowe, Nature (London), 1978, 272, 557 CAS.
  11. J. R. Dilworth, J. Hu, R. Thompson and D. L. Hughes, J. Chem. Soc., Chem. Commun., 1992, 551 RSC.
  12. T. E. Burrow, A. J. Lough, R. H. Morris and R. L. Richards, Can. J. Chem., 1995, 73, 1092 CAS.
  13. T. E. Burrow, A. J. Lough, R. H. Morris and R. L. Richards, Inorg. Chim. Acta, 1997, 259, 125 CrossRef CAS.
  14. International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. IV, pp. 99 and 149 Search PubMed.
  15. P. J. Blower, J. R. Dilworth, J. P. Hutchinson and J. A. Zubieta, J. Chem. Soc., Dalton Trans., 1985, 1533 RSC.
  16. A. L. Chaney and E. P. Marbach, Clin. Chem., 1962, 8, 130 CAS.
  17. G. W. Watt and J. D. Chrisp, Anal. Chem., 1952, 24, 2006 CrossRef CAS.
  18. G. M. Sheldrick, Acta Crystallogr., Sect. A, 1990, 46, 467 CrossRef.
  19. C. K. Fair, MOLEN, Structure Determination System, Enraf-Nonius, Delft, 1990.
  20. C. K. Johnson, ORTEP II, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
  21. G. M. Sheldrick, SHELX, Program for crystal structure determination, University of Cambridge, 1976; also SHELXN, an extended version, 1977.
  22. S. N. Anderson, R. L. Richards and D. L. Hughes, J. Chem. Soc., Dalton Trans., 1986, 245 RSC.
Click here to see how this site uses Cookies. View our privacy policy here.