Response to steric constraint in azacryptate and related complexes of iron-(II) and -(III)[hair space]*

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

F. Anthony Deeney, Charles J. Harding, Grace G. Morgan, Vickie McKee, Jane Nelson, Simon J. Teat and William Clegg


Abstract

Iron(II) cryptates, where the FeII is in the high-spin S = 2 electronic configuration, even with six sp2 N-donors, and iron(III) cryptates adopting the intermediate spin S = [/] state have been prepared. The structure of a high-spin iron(II) cryptate utilising six sp2 N-donors shows long metal–ligand distances which effectively destabilise the low-spin 1Ag configuration. Comparison is made between iron(III) cryptates, a less sterically constrained podand complex of the same donor set, and analogous N4O2 polychelates, which are respectively intermediate-, high- and low-spin or S = [/] ←→ S = ½ spin crossover systems. The Mössbauer spectra of the iron(III) cryptates and analogous podate are remarkably similar, despite their different spin states, suggesting covalency in the podate binding. The crystal structure of the podate supports this conclusion, as the iron–ligand donor distances are short for high-spin FeIII.


References

  1. See, for example, M. M. Bishop, J. Lewis, T. D. O'Donoghue, P. R. Raithby and J. N. Ramsden, J. Chem. Soc., Dalton Trans., 1980, 1390 Search PubMed; S. M. Nelson, P. Bryan and D. H. Busch, Chem. Commun., 1966, 641 RSC; S. M. Nelson and D. H. Busch, Inorg. Chem., 1969, 8, 1859 RSC; B. F. Hoskins, R. Robson and G. A. Williams, Inorg. Chim. Acta, 1976, 16, 121 CrossRef CAS.
  2. D. R. Boston and N. J. Rose, J. Am. Chem. Soc., 1968, 90, 6859 CrossRef CAS.
  3. N. Herron, M. Y. Chavan and D. H. Busch, J. Chem. Soc., Dalton Trans., 1984, 1491 RSC.
  4. (a) R. J. Motekaitis, A. E. Martell and W. Benutely, Inorg. Chim. Acta, 1993, 205, 23 CrossRef; (b) G. Morgan, Ph.D. Thesis, Open University, 1995.
  5. M. G. B. Drew, J. Hunter, D. J. Marrs, J. Nelson and C. J. Harding, J. Chem. Soc., Dalton Trans., 1992, 3235 RSC.
  6. J. Hunter, Ph.D. Thesis, Open University, 1991.
  7. S. J. Lippard, Angew. Chem., Int. Ed. Engl., 1988, 27, 344 CrossRef.
  8. K. N. Raymond, T. J. McMurry and T. M. Garrett, Pure Appl. Chem., 1988, 60, 545 CAS; K. N. Raymond and T. M. Garrett, Pure Appl. Chem., 1988, 60, 1807 CAS.
  9. M. G. B. Drew, C. J. Harding, G. G. Morgan, V. McKee and J. Nelson, J. Chem. Soc., Chem. Commun., 1995, 1035 RSC.
  10. P. Gutlich, A. Hauser and H. Speiring, Angew. Chem., Int. Ed. Engl., 1994, 33, 2024 CrossRef; P. Gutlich and A. Hauser, Coord. Chem. Rev., 1990, 97, 1 CrossRef.
  11. See, for example, (a) Q. Lu, J.-M. Latour, C. J. Harding, N. Martin, D. Marrs, V. McKee and J. Nelson, J. Chem. Soc., Dalton Trans., 1994, 649 Search PubMed; (b) M. G. B. Drew, O. Howarth, G. G. Morgan and J. Nelson, J. Chem. Soc., Dalton Trans., 1994, 3149 RSC; (c) G. G. Morgan, V. McKee and J. Nelson, Inorg. Chem., 1994, 33, 4427 CrossRef CAS and refs. therein.
  12. J. Hunter, C. J. Harding, M. McCann, V. McKee and J. Nelson, J. Chem. Soc., Chem. Commun., 1990, 1148 RSC and refs. therein.
  13. Q. Lu, C. J. Harding, V. McKee and J. Nelson, Inorg. Chim. Acta, 1993, 211, 195 CrossRef.
  14. R. Abidi, F. Arnaud-Neu, M. G. B. Drew, S. Lahely, D. J. Marrs, J. Nelson and M.-J. Schwing-Weil, J. Chem. Soc., Perkin Trans. 2, 1996, 2747 RSC.
  15. N. N. Greenwood and T. C. Gibb, Mössbauer Spectroscopy, Chapman and Hall, London, 1971 Search PubMed.
  16. L. J. Wilson and N. J. Rose, J. Am. Chem. Soc., 1968, 90, 6041 CrossRef CAS; C. Mealli and E. C. Lingafelter, J. Chem. Soc. D, 1970, 885 RSC; K. Boubeker, A. Deroche, F. Lambert and I. Morgenstern-Badarau, Acta Crystallogr., Sect. C, 1995, 51, 2244 CrossRef.
  17. E. B. Fleischer, A. E. Gebala, D. R. Swift and P. A. Tasker, Inorg. Chem., 1972, 11, 2775 CrossRef CAS.
  18. See, for example, M. G. B. Drew, M. McCann and S. M. Nelson, Inorg. Chim. Acta, 1980, 41, 213 Search PubMed; C. Cairns, S. M. Nelson and M. G. B. Drew, J. Chem. Soc., Dalton Trans., 1981, 1965 CrossRef CAS; L. Mazzarella, C. Pellecchia, C. A. Mattia, V. de Felice and R. Puliti, J. Coord. Chem., 1986, 14, 191 RSC; I. Vasilevsky, R. E. Stenkamp, E. C. Lingafelter and N. J. Rose, J. Coord. Chem., 1988, 19, 171 CAS; C. Piguet, G. Bernardinelli, A. F. Williams and B. Bocquet, Angew. Chem., Int. Ed. Engl., 1995, 34, 582 CAS; C. Scheer, P. Chautemps, I. Gautier-Luneau, J.-L. Pierre, G. Serratrice and E. Saint-Aman, Polyhedron, 1996, 15, 219 CrossRef CAS; S. Brooker and T. Simpson, J. Chem. Soc., Dalton Trans., 1998, 1151 CrossRef CAS.
  19. C. J. Harding, F. J. Mabbs, E. J. MacInnes, V. McKee and J. Nelson, J. Chem. Soc., Dalton Trans., 1996, 3227 RSC.
  20. Q. Lu, C. J. Harding, V. McKee and J. Nelson, J. Chem. Soc., Dalton Trans., 1993, 1768 Search PubMed.
  21. W. H. Armstrong and S. J. Lippard, J. Am. Chem. Soc., 1983, 105, 4837 CrossRef CAS; W. H. Armstrong, A. Spool, G. C. Papaefthymiou, R. B. Frankel and S. J. Lippard, J. Am. Chem. Soc., 1984, 106, 3653 CrossRef CAS; P. Chaudhuri, K. Wieghardt, B. Nuber and J. Weiss, Angew. Chem.,Int. Ed. Engl., 1985, 24, 778 CrossRef.
  22. Y. Dussart, A. Escuer, R. Vicente, C. J. Harding, J. Nelson and V. McKee, in preparation.
  23. (a) W. M. Marrit, Ph.D. Thesis, Cal Tech., 1982; (b) M. D. Timken, W. A. Marritt, D. N. Hendrickson, R. A. Gagné and E. Sinn, Inorg. Chem., 1985, 24, 4203.
  24. (a) E. Sinn, P. G. Sim, E. V. Dose, M. F. Tweedle and L. J. Wilson, J. Am. Chem. Soc., 1978, 100, 3375 CrossRef CAS; (b) M. F. Tweedle and L. J. Wilson, J. Am. Chem. Soc., 1976, 98, 4824 CrossRef CAS; (c) E. V. Dose, K. M. M. Murphy and L. J. Wilson, Inorg. Chem., 1976, 15, 2622 CrossRef CAS.
  25. M. M. Maltempo, J. Chem. Phys., 1974, 61, 2540 CrossRef CAS; J. S. Griffith, Mol. Phys., 1964, 8, 213 CAS.
  26. K. D. Hodges, R. G. Wollmann, S. L. Kessel, D. N. Hendrickson, D. G. Van Derveer and E. K. Barefield, J. Am. Chem. Soc., 1979, 101, 906 CrossRef CAS; H. Mosbaek and K. G. Poulsen, Acta Chem. Scand., 1971, 15, 2421.
  27. F. V. Wells, S. W. McCann, H. H. Wickman, S. L. Kessel, D. N. Hendrickson and R. D. Feltham, Inorg. Chem., 1982, 21, 2306 CrossRef CAS.
  28. H. Wickman and A. M. Trozzolo, Inorg. Chem., 1968, 7, 63 CrossRef CAS.
  29. (a) D. F. Cook, D. Cummins and E. D. McKenzie, J. Chem. Soc., Dalton Trans., 1976, 1369 RSC; (b) S. K. Chandra, P. Chakraborty and A. Chakravorty, J. Chem. Soc., Dalton Trans., 1993, 863 RSC.
  30. Y. Elerman, M. Kabak, I. Svoboda, H. Fuess and O. Atakal, J. Chem. Crystallogr., 1995, 25, 227 CAS.
  31. T. Ito, M. Sugimoto, H. Ito, K. Toriumi, H. Nakayama, W. Mori and M. Sakazaki, Chem. Lett., 1983, 121.
  32. R. S. Drago, Physical Methods in Chemistry, W. B. Saunders, Philadelphia, London, New York, 1977 Search PubMed.
  33. S. K. Chandra and A. Chakravorty, Inorg. Chem., 1991, 30, 3795 CrossRef CAS.
  34. M. G. B. Drew, V. Felix, G. Morgan, V. McKee and J. Nelson, J. Supramol. Chem., 1995, 5, 281 Search PubMed.
  35. J. Nelson and D. McDowell, Tetrahedron Lett., 1988, 385 CrossRef CAS; C. J. Harding, Q. Lu, D. J. Marrs, N. Martin, V. McKee and J. Nelson, J. Chem. Soc., Dalton Trans., 1995, 1739 RSC.
  36. G. M. Sheldrick, SHELXL 97, University of Göttingen, 1997.
Click here to see how this site uses Cookies. View our privacy policy here.