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Applied Magnetic Resonance

, Volume 20, Issue 1–2, pp 35–70 | Cite as

Probing the surrounding of a cobalt(II) porphyrin and its superoxo complex by EPR techniques

  • M. Baumgarten
  • C. J. Winscom
  • W. Lubitz
Article

Abstract

Octaethylporphyrinato-cobalt(II), Co(II)OEP, was studied by electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) in frozen solutions of methanol, tetrahydrofuran and pyridine diluted into chloroform. Oxygenation led to the respective paramagnetic superoxo complexes Co(III)OEP · py · O 2 −⋅ The EPR spectra demonstrate strong differences in the axial ligation states ((base-on)/(base-off)) and ease of the oxygenation process. Additional ENDOR studies with partial orientation selection along the principalg tensor axes are performed for resolution of the1H,14/15N and59Co hyperfine coupling constants. This allows a comparison of the electron spin density distribution of the superoxo complex and its precursor. The data are interpreted in the framework of a more rigorous and detailed theoretical configuration interaction model than previously presented in the literature. The theoretical treatment shows that the structure of the superoxo complex is best described in a three-orbital model with contributions from the cobalt 3d, 4s, and oxygen π orbitals. The analysis reproduces the experimentalg and Co hyperfine data yielding the relative energies of the MO’s and the MO coefficients for the description of the spin density distribution in the Co(II) complex and its superoxo complex. To demonstrate the generality of the approach and possible applications, a comparison is made with the vitamin B12r system. Furthermore, it provides detailed insight into the electronic and geometric changes resulting from axial ligation and oxygenation of the Co(II)OEP complex; this information can be used for predictions of the catalytic activity.

Keywords

Electron Paramagnetic Resonance Porphyrin Molecular Orbital Electron Paramagnetic Resonance Spectrum Spin Density 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. 1.
    Basolo F., Hoffman B.M., Ibers J.A.: Acc. Chem. Res.1975, 384–392.Google Scholar
  2. 2.
    Drago R.S.: Coord. Chem. Rev.32, 97–110 (1980)CrossRefGoogle Scholar
  3. 3.
    Subramanian J. in: Porphyrins and Metalloporphyrins (Smith K.M., ed.), pp. 555–589. Amsterdam: Elsevier 1975.Google Scholar
  4. 4.
    Sheldon R.A., Kochi J.K.: Metal Catalyzed Oxidations of Organic Compounds. New York: Academic Press 1981.Google Scholar
  5. 5.
    Daul C., Schläpfer C.W., von Zelewsky A.: Struct. Bonding36, 129 (1979)CrossRefGoogle Scholar
  6. 6.
    Martell A.E. (ed.): Coordination Chemistry (vol. 1), ACS Monograph, vol. 168. New York: Van Nostrand Reinhold Comp. 1971.Google Scholar
  7. 7.
    Walker F.A.: J. Am. Chem. Soc.95, 1154 (1973)CrossRefGoogle Scholar
  8. 8.
    Däges G.P., Hüttermann J.: J. Phys. Chem.96, 4787 (1992)CrossRefGoogle Scholar
  9. 9.
    van Doorslaer S., Bachmann R., Schweiger A.: J. Phys. Chem. B103, 5446 (1999)CrossRefGoogle Scholar
  10. 10.
    van Doorslaer S., Schweiger A.: J. Phys. Chem. B104, 2919 (2000)CrossRefGoogle Scholar
  11. 11.
    Bowen J.H., Shokhirev N.V., Raitsimring A.M., Buttlaire D.H., Walker F.A.: J. Phys. Chem. B101, 8683 (1997)CrossRefGoogle Scholar
  12. 12.
    Dolphin D. (ed.): B12. New York: Wiley 1982.Google Scholar
  13. 13.
    Zagalak P., Friedrich W. (eds.): Vitamin B12. Berlin: De Gruyter 1979.Google Scholar
  14. 14.
    Rao R.D.N., Symons M.C.R.: J. Chem. Soc. Perkin Trans.II 1983, 187; J. Chem. Soc. Faraday Trans.I 79, 269 (1983)Google Scholar
  15. 15.
    Bayston J.H., King N.K., Looney F.D., Winfield M.E.: J. Am. Chem. Soc.91, 2775 (1969)CrossRefGoogle Scholar
  16. 16.
    Jörin E., Schweiger A., Günthard Hs.H.: Chem. Phys. Lett.61, 228 (1979)CrossRefADSGoogle Scholar
  17. 17.
    James B.R. in: The Porphyrins (Dolphin D., ed.), vol. 5, pp. 207 ff. New York: Academic Press 1979.Google Scholar
  18. 18.
    Jones R.D., Summerville D.A., Basolo F.: Chem. Rev.79, 139–179 (1979)CrossRefGoogle Scholar
  19. 19.
    Spiro T.E. (ed.): Metal Ion Activation of Dioxygen. New York: Wiley 1980.Google Scholar
  20. 20.
    Hill C.J. (ed.): Activation and Functionalization of Alkanes. New York: Wiley 1989.Google Scholar
  21. 21.
    Vigato P.A., Tamburini S., Fenton D.E.: Coord. Chem. Rev.106, 25 (1990)CrossRefGoogle Scholar
  22. 22.
    Hamilton D.E., Drago R.S., Zombeck A.: J. Am. Chem. Soc.109, 374 (1987)CrossRefGoogle Scholar
  23. 23.
    Sobkowiak A., Sawyer D.T.: J. Am. Chem. Soc.113, 9520 (1991)CrossRefGoogle Scholar
  24. 24.
    Suzuki Y., Nishide H., Tsuchida E.: Macromolecules33, 2530 (2000)CrossRefADSGoogle Scholar
  25. 25.
    Nishide H., Tsuchida E. in: Macromolecular Complexes (Tsuchida E., ed.), pp. 119 ff. Weinheim: VCH 1991.Google Scholar
  26. 26.
    Chien J.C.W., Dickinson L.C. in: Biological Magnetic Resonance (Berliner L.J., Reuben J., eds.), vol. 3, chap. 4, p. 155. New York: Plenum Press 1981.Google Scholar
  27. 27.
    Dolphin D. (ed.): The Porphyrins, vol. 1–7. New York: Academic Press 1978, 1979.Google Scholar
  28. 28.
    Walker F.A.: J. Magn. Reson.15, 201 (1974); Walker F.A., Reis D., Blake V.L.: J. Am. Chem. Soc.106, 6888–6898 (1984); Walker F.A., Brown J.: J. Am. Chem. Soc.107, 7632 (1985)Google Scholar
  29. 29.
    Tovrog B.S., Kitko D.J., Drago R.S.: J. Am. Chem. Soc.98, 5144 (1976)CrossRefGoogle Scholar
  30. 30.
    Hoffman B.M., Diemente D.L., Basolo F.J.: J. Am. Chem. Soc.92, 61 (1970)CrossRefGoogle Scholar
  31. 31.
    Smith T.D., Pilbrow J.R.: Coord. Chem. Rev.39, 295–383 (1981)Google Scholar
  32. 32.
    Getz D., Melamud E., Silver B.L., Dori Z.: J. Am. Chem. Soc.97, 3846 (1975)CrossRefGoogle Scholar
  33. 33.
    Jörin E., Schweiger A., Günthard Hs.H.: J. Am. Chem. Soc.105, 4277–4286 (1983)CrossRefGoogle Scholar
  34. 34.
    Schweiger A.: Struct. Bonding51, 1 (1982)CrossRefGoogle Scholar
  35. 35.
    Schweiger A.: Electron Spin Reson.10, 138–185 (1987)CrossRefADSGoogle Scholar
  36. 36.
    Rist G.H., Hyde J.S.: J. Chem. Phys.52, 4633–4643 (1970)CrossRefADSGoogle Scholar
  37. 37.
    Möbius K., Lubitz W. in: Biological Magnetic Resonance (Berliner L.J., Reuben J., eds.), vol. 7, chap. 3, pp. 129–247. New York: Plenum Press 1987.Google Scholar
  38. 38.
    Stach J., Böttcher R., Kirmse R.: Z. Chem.25, 1 (1985)Google Scholar
  39. 39.
    Baumgarten M., Lubitz W., Winscom C.J.: Chem. Phys. Lett.133, 102 (1987)CrossRefADSGoogle Scholar
  40. 40.
    Hurst G.C., Henderson T.A., Kreilick R.W.: J. Am. Chem. Soc.107, 7294, 7299 (1985)CrossRefGoogle Scholar
  41. 41.
    Greiner S.P., Kreilick R.W., Kraft K.A.: J. Am. Chem. Soc.114, 391–399 (1992)CrossRefGoogle Scholar
  42. 42.
    Greiner S.P., Rowlands D.L., Kreilick R.W.: J. Phys. Chem.96, 9132–9139 (1992)CrossRefGoogle Scholar
  43. 43.
    Kirste B., van Willigen H.: J. Phys. Chem.87, 781–788 (1983)CrossRefGoogle Scholar
  44. 44.
    McGarvey B.: Can. J. Chem.53, 2498 (1975); McGarvey B.: Can. J. Chem.53, 3791 (1975)CrossRefGoogle Scholar
  45. 45.
    Fleischer E.B.: Inorg. Chem.3, 493 (1962)CrossRefGoogle Scholar
  46. 46.
    Fuhrhop J.H., Smith K.M. in: Porphyrins and Metalloporphyrins (Smith K.M., ed.), p. 757. Amsterdam: Elsevier 1975.Google Scholar
  47. 47.
    Gouterman M. in: The Porphyrins (Dolphin D., ed.), vol. 3, pp. 1–165. New York: Academic Press 1979.Google Scholar
  48. 48.
    Segal B.G., Kaplan M., Fraenkel G.K.: J. Chem. Phys.43, 4191 (1965)CrossRefADSGoogle Scholar
  49. 49.
    Kurreck H., Kirste B., Lubitz W. in: Stereochemical Analysis (Marchand A.P., ed.), chap. 2.4. New York: VCH Publishers 1988.Google Scholar
  50. 50.
    Lendzian F.: Ph. D. Thesis, Freie Universität Berlin, Berlin, Germany 1982.Google Scholar
  51. 51.
    Baumgarten M.: Ph. D. Thesis, Freie Universität Berlin, Berlin, Germany 1988.Google Scholar
  52. 52.
    Winscom C.J., Atherton N.M.: Inorg. Chem.12, 383 (1973)CrossRefGoogle Scholar
  53. 53.
    Lubitz W., Winscom C.J., Diegruber H., Möseler R.: Z. Naturforsch.42 a, 970 (1987)Google Scholar
  54. 54.
    Lin W.C.: Inorg. Chem.19, 1072 (1980)CrossRefGoogle Scholar
  55. 55.
    Iwaizumi M., Ohba Y., Ilda H., Hirayama M.: Inorg. Chim. Acta.82, 47–52 (1984)CrossRefGoogle Scholar
  56. 56.
    Greiner S.P., Baumgarten M.: J. Magn. Reson.83, 630 (1989); Greiner S.P.: Ph. D. Thesis, University of Rochester, Rochester, N.Y., USA, 1987.Google Scholar
  57. 57.
    Lancashire R.L., Smith T.D., Pilbrow J.A.: J. Chem. Soc. Dalton Trans.1979, 66.Google Scholar
  58. 58.
    Höhn M., Hüttermann J.: J. Biol. Chem.257, 10554 (1982)Google Scholar
  59. 59.
    Clementi E.: J. Chem. Phys.41, 295 (1964)CrossRefADSGoogle Scholar
  60. 60.
    Abragam A., Pryce M.H.L.: Proc. R. Soc. Lond. A206, 173 (1951)zbMATHCrossRefADSGoogle Scholar
  61. 61.
    Dunn T.M.: Trans. Faraday Soc.57, 144 (1961)Google Scholar
  62. 62.
    Horsefield A., Morton J.R., Rowlands J.R., Whiffen D.H.: Mol. Phys.5, 241 (1962)CrossRefADSGoogle Scholar
  63. 63.
    Hsieh Y.-N., Rubenacker G.V., Cheng C.P., Brown T.L.: J. Am. Chem. Soc.99, 1384 (1977)CrossRefGoogle Scholar
  64. 64.
    Brown T.G., Hoffman B.M.: Mol. Phys.39, 1073 (1980)CrossRefADSGoogle Scholar
  65. 65.
    Longuet-Higgins H.C., Pople J.A.: Proc. Phys. Soc. A68, 591 (1955)CrossRefADSGoogle Scholar
  66. 66.
    Hinchliffe A.H.: Theor. Chim. Acta5, 208 (1966); Hinchliffe A.H., Ali M.A.: Theor. Chim. Acta5, 271 (1966)CrossRefGoogle Scholar
  67. 67.
    Scholz M., Köhler H.-J.: Quantenchemie, Band 3. Berlin: VEB Deutscher Verlag der Wissenschaften 1981.Google Scholar
  68. 68.
    Schweiger A., Jörin E., Günthard Hs.H.: Chem. Phys. Lett.61, 223 (1979)CrossRefADSGoogle Scholar
  69. 69.
    Duchstein H.-J., Baumgarten M.: Arch. Pharm.321, 781–785 (1988)CrossRefGoogle Scholar
  70. 70.
    Kasai P.H., Bishop R.J. Jr. in: Zeolite Chemistry and Catalysis (Rabo J.A., ed.). ACS Monograph, vol. 171, 350. Washington: American Chemical Society 1976.Google Scholar

Copyright information

© Springer-Verlag 2001

Authors and Affiliations

  • M. Baumgarten
    • 1
  • C. J. Winscom
    • 2
  • W. Lubitz
    • 3
  1. 1.Max-Planck-Institut für PolymerforschungMainzGermany
  2. 2.Kodak R&D LtdHarrowGreat Britain
  3. 3.Max-Volmer-Institut für Biophysikalische Chemie und BiochemieTechnische Universität BerlinBerlinGermany

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