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DOI: 10.1039/A703678G (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 4119-4126

A novel hexaaza macrocycle with methylenephosphonate pendant arms: a potential useful chelate for biomedical applications[hair space]†

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S. W. Annie Bligh, Nick Choi, Carlos F. G. C. Geraldes, Stefan Knoke, Mary McPartlin, Mahesh J. Sanganee and Thomas M. Woodroffe

Abstract

A new 18-membered hexaaza macrocyclic ligand with four pendant methylenephosphonates has been synthesized via the Mannich reaction. The protonation behaviour of this macrocycle has been followed by 31P and 1H NMR spectroscopy. The initial protonation pattern of the N-functionalised macrocycle is rather like its corresponding macrocyclic amine. The proton NMR spectrum of its lanthanum(III) complex in aqueous solution indicates that the complex adopts only one of the five possible conformations, either SSSS or RRRR. The crystal structure of the novel macrocyclic ligand shows an extended hydrogen-bonded structure in its solid state. The macrocycle has an unusual conformation with the pendants alternating ‘up’ and ‘down’ round the ring. The LaIII complex has a unique ten-co-ordinate geometry with all pendant arms co-ordinated to the LaIII ion which is in the plane of the six macrocyclic nitrogen donors.

References

  1. M. F. Loncin, J. F. Desreux and E. Merciny, Inorg. Chem., 1986, 25, 2646 CrossRef CAS.
  2. A. D. Sherry, J. Ren, J. Huskens, E. Brücher, E. Tóth, C. F. G. C. Geraldes, M. M. C. A. Castro and W. P. Cacheris, Inorg. Chem., 1996, 35, 4604 CrossRef CAS.
  3. C. F. G. C. Geraldes, A. D. Sherry and G. E. Kiefer, J. Magn. Reson., 1992, 97, 290.S.
  4. S. Aime, M. Botta, E. Terreno, P. L. Anelli and F. Uggeri, Magn. Reson. Med., 1993, 30, 583 CrossRef CAS.
  5. L. R. Dick, C. F. G. C. Geraldes, A. D. Sherry, C. W. Gray and D. M. Gray, Biochemistry, 1989, 28, 7896 CrossRef.
  6. D. W. Swinkels, J. P. M. van Duynhoven, C. W. Hilbers and G. I. Tesser, Recl. Trav. Chim. Pays-Bas, 1991, 110, 124 CAS.
  7. N. Bansal, M. J. Germann, V. Seshan, G. T. Shires III, C. R. Malloy and A. D. Sherry, Biochemistry, 1993, 32, 5638 CrossRef CAS.
  8. V. Seshan, M. J. Germann, P. Preisig, C. R. Malloy, A. D. Sherry and N. Bansal, Magn. Reson. Med., 1995, 34, 25 CrossRef CAS.
  9. S. W. A. Bligh, N. Choi, W. J. Cummins, E. G. Evagorou, J. D. Kelly and M. McPartlin, J. Chem. Soc., Dalton Trans., 1993, 3829 RSC.
  10. C. F. G. C. Geraldes, A. D. Sherry and W. P. Cacheris, Inorg. Chem., 1989, 28, 3336 CrossRef CAS.
  11. G. L. Rothermel, jun., L. Miao, A. L. Hill and S. C. Jackels, Inorg. Chem., 1992, 31, 4854 CrossRef.
  12. J. L. Sudmeier and C. N. Reilley, Anal. Chem., 1964, 36, 1698 CrossRef CAS.
  13. W. Clegg, P. B. Iveson and J. C. Lockhart, J. Chem. Soc., Dalton Trans., 1992, 3291 RSC.
  14. I. Lázár, D. C. Hrncir, W.-D. Kim, G. E. Kiefer and A. D. Sherry, Inorg. Chem., 1992, 31, 4422 CrossRef CAS.
  15. G. V. Polyanchuk, L. M. Shkol'nikova, M. V. Rudomino, N. M. Dyatlova and S. S. Makarevich, Zh. Strukt. Khim., 1985, 26, 109 Search PubMed.
  16. N. Y. C. Choi, Ph.D. Thesis, University of North London, 1996.
  17. V. Alexander, Chem. Rev., 1995, 95, 273 CrossRef CAS.
  18. C. F. G. C. Geraldes, R. D. Brown III, W. P. Cacheris, S. H. Koenig, A. D. Sherry and M. Spiller, Magn. Reson. Med., 1989, 9, 94 CAS.
  19. N. W. Alcock, R. G. Kingston, P. Moore and C. Pierpoint, J. Chem. Soc., Dalton Trans., 1984, 1937 RSC.
  20. P. K. Glasoe and F. A. Long, J. Phys. Chem., 1960, 64, 188 CrossRef CAS.
  21. SHELXTL, PC version 5.03, Siemens Analytical Instruments Inc., Madison, WI, 1994.
  22. S. R. Parkin, B. Moezzi and H. Hope, XABS 2, J. Appl. Crystallogr., 1995, 28, 53 CrossRef CAS.
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