Preparation and reactions of rhenium(VII) trioxo hydrogendiolato complexes and rhenium(VI) oxo bis(diolato) complexes

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

Peter G. Edwards, Jukka Jokela, Ari Lehtonen and Reijo Sillanpää


Abstract

The compound Re2O7, Re2O7·2H2O or [ReO3(OSiMe3)] reacted with H2diol to form complexes having the general formula [ReO3(Hdiol)] where H2diol = 2,3-dimethylbutane-2,3-diol (H2pin) or 1,1′-bicyclohexane-1,1′-diol (H2bicy). In the case of H2pin the complex [ReO3(Hpin)]·H2pin is formed initially in the reaction of rhenium(VII) oxides with an excess of pinacol. The hydrogen bonded free pinacol molecule can be removed by sublimation. The monomethyl derivative of pinacol, HMepin, reacts in a similar way to form the complex [ReO3(Mepin)]. In the rhenium(VII) compounds the Re atom has a distorted trigonal bipyramidal co-ordination geometry. Pale yellow solutions of [ReO3(Hdiol)] in CH2Cl2 slowly become orange and red crystals having the formula [ReO(diol)2] may be isolated. The reaction of rhenium(VII) oxides with H2diol and PPh3 in the presence of drying agents in CH2Cl2 produced the same compounds in high yield. The crystal structures of the rhenium(VI) complexes reveal that the rhenium(VI) cations have square pyramidal co-ordination geometries. The rhenium(VI) oxo bis(diolato) complexes are thermally stable and do not readily undergo oxidation in dry air.


References

  1. C. C. Romão, F. E. Kühn and W. A. Herrmann, Chem. Rev., 1997, 97, 3197 CrossRef CAS; W. A. Herrmann and F. E. Kühn, Acc. Chem. Res., 1997, 30, 169 CrossRef CAS.
  2. Z. Zhu and J. H. Espenson, Organometallics, 1997, 16, 3658 CrossRef CAS.
  3. A. K. Yudin and K. B. Sharpless, J. Am. Chem. Soc., 1997, 119, 11536 CrossRef CAS.
  4. P. Edwards and G. Wilkinson, J. Chem. Soc., Dalton Trans., 1984, 2695 RSC.
  5. T. B. Towne and F. E. McDonald, J. Am. Chem. Soc., 1997, 119, 6022 CrossRef CAS.
  6. W. A. Herrmann, W. A. Wojtczak, G. R. Artus, F. E. Kühn and M. R. Mattner, Inorg. Chem., 1997, 36, 465 CrossRef CAS.
  7. P. G. Edwards, A. C. Skapski, A. M. Z. Slawin and G. Wilkinson, Polyhedron, 1984, 3, 1083 CrossRef.
  8. J. W. Johnson, J. F. Brody, G. B. Ansell and S. Zentz, Inorg. Chem., 1984, 23, 2415 CrossRef CAS.
  9. P. G. Edwards, G. Wilkinson, M. B. Hursthouse and K. M. A. Malik, J. Chem. Soc., Dalton Trans., 1980, 2467 RSC.
  10. E. Jacob, Angew. Chem., Int. Ed. Engl., 1982, 21, 142 CrossRef.
  11. L. A. de Larie, R. C. Haltiwanger and C. G. Pierpont, Inorg. Chem., 1987, 26, 817 CrossRef CAS.
  12. W. A. Herrmann, P. Watzlowik and P. Kiprof, Chem. Ber., 1991, 124, 1101 CAS.
  13. K. Mertis, D. H. Williamson and G. Wilkinson, J. Chem. Soc., Dalton Trans., 1975, 607 RSC.
  14. K. Mertis and G. Wilkinson, J. Chem. Soc., Dalton Trans., 1976, 1488 RSC.
  15. W. A. Herrmann and P. Watzlowik, J. Organomet. Chem., 1992, 437, 363 CrossRef CAS.
  16. J. Mink, G. Kresztury, A. Stirling and W. A. Herrmann, Spectrochim. Acta, Part A, 1994, 50, 2039 CrossRef.
  17. R. J. Collin, J. Jones and W. P. Griffith, J. Chem. Soc., Dalton Trans., 1974, 1094 RSC.
  18. The Sadtler handbook of proton NMR spectra, ed. W. W. Simons, Sadtler, Philadelphia, 1978, p. 978 Search PubMed.
  19. C. K. Johnson, ORTEP II, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
  20. W. A. Hermann, F. E. Kühn, M. U. Rauch, J. D. G. Correia and G. Artus, Inorg. Chem., 1995, 34, 2914 CrossRef CAS.
  21. T. M. Trnka and G. Parkin, Polyhedron, 1997, 16, 1031 CrossRef CAS.
  22. J. Matheson and B. R. Penfold, Acta Cryst., Sect. B, 1979, 35, 2707 CrossRef.
  23. A. Lehtonen and R. Sillanpää, J. Chem. Soc., Dalton Trans., 1994, 2119 RSC.
  24. L. O. Atovmyan and Y. A. Sokolova, Zh. Strukt. Khim., 1979, 20, 754 Search PubMed.
  25. F. L. Phillips and A. C. Skapski, Acta Crystallogr., Sect B, 1975, 21, 212.
  26. D. Melaven, J. N. Fowle, W. Brickell and C. F. Hiskey, Inorg. Synth., 1950, 2, 188.
  27. M. Schmidt and H. Schmidbaur, Inorg. Synth., 1967, 9, 149 CAS.
  28. E. J. Corey, R. L. Danheiser and S. Chandrasekaran, J. Org. Chem., 1976, 41, 260 CrossRef CAS.
  29. A. C. T. North, D. C. Phillips and F. S. Mathews, Acta Crystallogr., Sect. A, 1968, 24, 351 CrossRef.
  30. W. H. Zachariazen, Acta Crystallogr., Sect A, 1968, 24, 212 CrossRef.
  31. TEXSAN-TEXRAY, Single Crystal Structure Analysis Package, Version 5.0, Molecular Structure Corporation, The Woodlands, Texas, 1989.
  32. G. M. Sheldrick, SHELXL 97, University of Göttingen, 1997.
  33. L. J. Farrugia, J. Appl. Crystallogr., 1997, 30, 565 CrossRef CAS.
Click here to see how this site uses Cookies. View our privacy policy here.