View PDF Version
 
DOI: 10.1039/A703842I (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 4595-4602

Dinuclear complexes of MnII, CoII and ZnII triply bridged by carboxylate groups: structures, properties and catalase-like function[hair space]‡

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

Masako Yamami, Megumi Tanaka, Hiroshi Sakiyama, Takeichiro Koga, Kensuke Kobayashi, Hitoshi Miyasaka, Masaaki Ohba and Hisashi Ōkawa

Abstract

1,3-Bis[(2-dimethylaminoethyl)iminomethyl]benzene (baib), having two isolated metal-binding sites separated by a m-xylenylene group, formed dinuclear metal(II) complexes [Mn2(baib)(O2CPh)3]BPh4·MeCN 1, [Mn2(baib)(O2CPh)3(NCS)] 2, [Co2(baib)(O2CMe)3]BPh4 3, [Co2(baib)(O2CPh)3]BPh4 4 and [Zn2(baib)(O2CMe)3]BPh4 5. The structure of a dimethylformamide adduct of 2, [Mn2(baib)(O2CPh)3(NCS)]·dmf 2′, was determined. It has a dinuclear core bridged by two benzoate groups in the symmetric η1:η1 mode and one benzoate group in the asymmetric η1:η2 mode, with a Mn[hair space][hair space]· · ·[hair space][hair space]Mn separation of 3.501(4) Å. A thiocyanate ion co-ordinates to one Mn through its nitrogen; both manganese ions are six-co-ordinated. Complex 3 was also characterized crystallographically. The pair of cobalt ions are bridged by three acetate groups in the η1:η1 mode with a Co[hair space][hair space]· · ·[hair space][hair space]Co intermetallic separation of 3.449(2) Å. The geometry about each Co is a trigonal bipyramid. The complexes 4·MeCN (4′) and 5 have dinuclear cores essentially similar to that of 3: Co[hair space][hair space]· · ·[hair space][hair space]Co 3.482(2) and Zn[hair space][hair space]· · ·[hair space][hair space]Zn 3.4648(7) Å. The physicochemical properties of the complexes are reported together with the catalase-like function of 1–3.

References

  1. D. E. Fenton and H. Ōkawa, Perspectives on Bioinorganic Chemistry, eds. R. W. Hay, J. R. Dilworth and K. B. Nolan, JAI Press, London, 1993, vol. 2, pp. 81–138 Search PubMed.
  2. M. A. Holms, I. LeTrong, S. Turkey, L. C. Sleker and R. E. Stenkamp, J. Mol. Biol., 1991, 218, 583.
  3. P. Nordlund, B.-M. Sjoberg and H. Eklund, Nature (London), 1990, 345, 593 CrossRef CAS.
  4. E. Hough, L. K. Hansen, B. Birknes, K. Jynge, S. Hansen, A. Hordvik, C. Little, E. J. Dodson and Z. Derewenda, Nature (London), 1989, 338, 357 CrossRef CAS.
  5. K. Wieghardt, Angew. Chem., Int. Ed. Engl., 1989, 28, 1153 CrossRef.
  6. H. Sakiyama, H. Tamaki, M. Kodera, N. Matsumoto and H. Ōkawa, J. Chem. Soc., Dalton Trans., 1993, 591 RSC.
  7. H. Sakiyama, H. Ōkawa and R. Isobe, J. Chem. Soc., Chem. Commun., 1993, 882 RSC; H. Sakiyama, H. Ōkawa and M. Suzuki, J. Chem. Soc., Dalton Trans., 1993, 3823 RSC.
  8. C. Higuchi, H. Sakiyama, H. Ōkawa, R. Isobe and D. E. Fenton, J. Chem. Soc., Dalton Trans., 1994, 1097 RSC.
  9. C. Higuchi, H. Sakiyama, H. Ōkawa and D. E. Fenton, J. Chem. Soc., Dalton Trans., 1995, 4015 RSC.
  10. N. F. Curtis, J. Chem. Soc., 1961, 3147 Search PubMed.
  11. E. A. Boudreaux and L. N. Mulay, Theory and Applications of Molecular Paramagnetism, Wiley, New York, 1976, pp. 491–494 Search PubMed.
  12. D. T. Cromer and J. T. Waber, International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4 Search PubMed.
  13. D. C. Creagh and W. J. McAuley, International Tables for Crystallography, Kluwer, Boston, 1992, vol. C, pp. 219–222 Search PubMed.
  14. D. C. Creagh and H. H. Hubbell, International Tables for Crystallography, Kluwer, Boston, 1992, vol. C, pp. 200–206 Search PubMed.
  15. TEXSAN, Molecular Structure Corporation, Houston, TX, 1985.
  16. C. K. Johnson, ORTEP, Report 3794, Oak Ridge National Laboratory, Oak Ridge, TN, 1965.
  17. P. W. Anderson, Solid State Phys., 1963, 14, 61 Search PubMed; H. M. McConnell, J. Chem. Phys., 1963, 39, 1910 CrossRef CAS.
  18. L. Sacconi, M. Ciampolini and G. P. Speroni, J. Am. Chem. Soc., 1965, 87, 3102 CrossRef CAS.
  19. H. Wada, K. Motoda, M. Ohba, H. Sakiyama, N. Matsumoto and H. Ōkawa, Bull. Chem. Soc. Jpn., 1995, 68, 1105 CAS.
  20. T. Aono, H. Wada, M. Yonemura, M. Ohba, H. Ōkawa and D. E. Fenton, J. Chem. Soc., Dalton Trans., 1997, 1527 RSC.