Characterization and Properties of Non-Heme Iron Peroxo Complexes

  • Jean-Jacques Girerd
  • Frédéric Banse
  • Ariane Jalila Simaan
Part of the Structure and Bonding book series (STRUCTURE, volume 97)


Iron-peroxo Fe(III)O2 and hydroperoxo Fe(III)OOH systems are important intermediates between the initial Fe(II)-dioxygen adduct and the “activated” form of the catalytic site in many mono-iron biomolecules. To the same peroxidic level correspond, in diiron enzymes, bridged peroxo Fe(III)-O-O-Fe(III) intermediates. This review is concerned with the preparation and spectroscopic characterization of such intermediates in non-heme chemical systems, the properties of the natural systems being quoted as references. Although none have been crystallized, it seems very likely that Fe(III)OOH systems present a η 1 - coordination mode for the hydroperoxo group. These Fe(III)OOH units have given clear signatures in UV-vis, resonance Raman and mass spectrometry. By EPR it was found that in Fe(III)OOH, the Fe(III) is low-spin (S = 1/2) and we propose here a simple rationalization of the characteristics of the EPR g-tensor. The electronic properties of the Fe(III)(η1-OOH) known so far, point toward a strong Fe-O bond and a weak O-O bond, in total agreement with the reactivity scheme implying a cleavage of the O-O bond to lead formally to a Fe(V)O unit. Alkylperoxo systems are also included in this review. Fe(III)-peroxo systems Fe(III)O2 have been prepared and described. They contain high-spin Fe(III) and those identified seem to be of the η 2 type. The Fe-O bond is weaker and the O-O one is stronger than in the Fe(III)OOH systems. The implication of these Fe(III)O2 units in catalysis is unclear. “Complementary” systems, such as Fe(III)(η 1-OO) or Fe(III)(η 2-OOH) have been evoked in publications but not identified spectroscopically. These systems certainly deserve to be actively looked for.


Peroxo complexes Iron Non-Heme EPR Resonance Raman UV-vis 


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  1. 1.
    Lippard SJ, Berg JM (1994) Principles of bioinorganic chemistry. University Science Books, Mill ValleyGoogle Scholar
  2. 2.
    Sono M, Roach MP, Coulter ED, Dawson JH (1996) Chem Rev 96: 2841CrossRefGoogle Scholar
  3. 3.
    Ferguson-Miller S, Babcock GT (1996) Chem Rev 96: 2889CrossRefGoogle Scholar
  4. 4.
    Wallar BJ, Lipscomb JD (1996) Chem Rev 96: 2625CrossRefGoogle Scholar
  5. 5.
    Que L, Ho RYN (1996) Chem Rev 96: 2607CrossRefGoogle Scholar
  6. 6.
    Sam JW, Tang XJ, Peisach J (1994) J Am Chem Soc 116: 5250CrossRefGoogle Scholar
  7. 7.
    Mizoguchi TJ, Lippard SJ (1998) J Am Chem Soc 120: 11022CrossRefGoogle Scholar
  8. 8.
    Simaan AJ et al., Eur J Inorg Chem, in pressGoogle Scholar
  9. 9.
    Bernai I, Jensen IM, Jensen KB, McKenzie CJ, Toftlund H, Tuchagues JP (1995) J Chem Soc Dalton Trans. 3667Google Scholar
  10. 10.
    Mialane P, Nivorojkine A, Pratviel G, Azéma L, Slany M, Godde F, Simaan A, Banse F, Kargar-Grisel T, Bouchoux G, Sainton J, Horner O, Guilhem J, Tchertanova L, Meunier B, Girerd JJ (1999) Inorg Chem 38: 1085CrossRefGoogle Scholar
  11. 11.
    Jensen KB, McKenzie CJ, Nielsen LP, Pedersen JZ, Svendsen HM (1999) Chem Commun 1313Google Scholar
  12. 12.
    Lubben M, Meetsma A, Wilkinson EC, Feringa B, Que L (1995) Angew Chem Int Ed Engl 34: 1512CrossRefGoogle Scholar
  13. 13.
    Ho RYN, Roelfes G, Feringa BL, Que L (1999) J Am Chem Soc 121: 264CrossRefGoogle Scholar
  14. 14.
    Roelfes G, Lubben M, Chen K, Ho RYN, Meestma A, Genseberger S, Hermant RM, Hage R, Mandai SK, Young VG, Zang Y, Kooijman H, Spek AL, Que L, Feringa BL (1999) Inorg Chem 38: 1929CrossRefGoogle Scholar
  15. 15.
    deVries ME, LaCrois RM, Roelfes G, Kooijman H, Spek AL, Hage R, Feringa BL (1997) Chem Commun 1549Google Scholar
  16. 16.
    Lippai I, Magliozzo RS, Peisach J (1999) J Am Chem Soc 121: 780CrossRefGoogle Scholar
  17. 17.
    Sauer-Masarwa A, Herron N, Fendrick CM, Busch DH (1993) Inorg Chem 32: 1086CrossRefGoogle Scholar
  18. 18.
    Kim C, Chen K, Kim J, Que L (1997) J Am Chem Soc 119: 5964CrossRefGoogle Scholar
  19. 19.
    Burger RM, Horwitz SB, Peisach J, Wittenberg JB (1979) J of Biol Chem 254: 12,299Google Scholar
  20. 20.
    Sobolev AP, Babushkin DE, Talsi EP (1996) Mendeleev Commun 236Google Scholar
  21. 21.
    Griffith JS (1961) The theory of transition metal ions. Cambridge University Press, LondonGoogle Scholar
  22. 22.
    Taylor CPS (1977) Biochimica et Biophysica Acta 491: 137Google Scholar
  23. 23.
    Veselov A, Sun H, Sienkiewicz A, Taylor H, Burger RM, Scholes CP (1995) J Am Chem Soc 117: 7508CrossRefGoogle Scholar
  24. 24.
    Hori H (1971) Biochimica et Biophysica Acta 251: 227Google Scholar
  25. 25. (a)
    Brunold TC, Solomon EI (1999) J Am Chem Soc 121: 8277CrossRefGoogle Scholar
  26. 25. (b)
    Brunold TC, Solomon EI (1999) J Am Chem Soc 121: 8288CrossRefGoogle Scholar
  27. 26.
    Shiemke AK, Loehr TM, Sanders-Loehr J (1984) J Am Chem Soc 106: 4951CrossRefGoogle Scholar
  28. 27.
    Kurtz DM, Shriver DF, Klotz IM (1976) J Am Chem Soc 98: 5033CrossRefGoogle Scholar
  29. 28.
    Guajardo RJ, Hudson SE, Brown SJ, Mascharak PK (1993) J Am Chem Soc 115: 7971CrossRefGoogle Scholar
  30. 29.
    Chen K, Que L (1999) Chem Commun 1375Google Scholar
  31. 30.
    Chen K, Que L (1999) Angew Chem Int Ed Engl 38: 2227CrossRefGoogle Scholar
  32. 31.
    Wada H, Ogo S, Watanabe Y, Mukai M, Kitagawa T, Jitsukawa K, Masuda H, Einaga H (1999) Inorg Chem 38: 3592CrossRefGoogle Scholar
  33. 32.
    Zang Y, Elgren TE, Dong Y, Que L (1993) J Am Chem Soc 115: 811CrossRefGoogle Scholar
  34. 33.
    Zang Y, Kim J, Dong Y, Wilkinson EC, Appleman EH, Que L (1997) J Am Chem Soc 119: 4197CrossRefGoogle Scholar
  35. 34.
    Lange SJ, Miyake H, Que L (1999) J Am Chem Soc 121: 6330CrossRefGoogle Scholar
  36. 35.
    Kim J, Larka E, Wilkinson EC, Que L (1995) Ang. Chem Int Ed Engl 34: 2048CrossRefGoogle Scholar
  37. 36.
    Ménage S, Wilkinson EC, Que L, Fontecave M (1995) Angew Chem Int Ed Engl 34: 203CrossRefGoogle Scholar
  38. 37.
    Nguyen C, Guajardo RJ, Mascharak PK (1996) Inorg Chem 35: 6273CrossRefGoogle Scholar
  39. 38.
    MacFaul PA, Ingold KU, Wayner DDM, Que L (1997) J Am Chem Soc 119: 10,594CrossRefGoogle Scholar
  40. 39.
    Walling C, Kurz M, Schugar HJ (1970) Inorg Chem 9: 931CrossRefGoogle Scholar
  41. 40.
    Ahmad S, McCallum JD, Shiemke AK, Appelman EH, Loehr TM, Sanders-Loehr J (1988) Inorg Chem 27: 2230CrossRefGoogle Scholar
  42. 41.
    Neese F, Solomon EI (1998) J Am Chem Soc 120: 12,829CrossRefGoogle Scholar
  43. 42.
    Simaan AJ, Banse F, Mialane P, Boussac A, Un S, Kargar-Grisel T, Bouchoux G, Girerd JJ (1999) Eur J Inorg Chem 993Google Scholar
  44. 43.
    Kim K, Lippard SJ (1996) J Am Chem Soc 118: 4914CrossRefGoogle Scholar
  45. 44.
    Ookubo T, Sugimoto H, Nagayama T, Masuda H, Sato T, Tanaka K, Maeda Y, Okawa H, Hayashi Y, Uehara A, Suzuki M (1996) J Am Chem Soc 118: 701CrossRefGoogle Scholar
  46. 45.
    Dong Y, Yan S, Young VG, Que L (1996) Angew Chem Int Ed Engl 35: 618CrossRefGoogle Scholar
  47. 46.
    Brunold TC, Tamura N, Kitajima N, Moro-oka Y, Solomon EI (1998) J Am Chem Soc 120: 5674CrossRefGoogle Scholar
  48. 47.
    Brennan BA, Chen Q, Juarez-Garcia C, True AE, O’Connor CJ, Que L (1991) Inorg Chem 30: 1937CrossRefGoogle Scholar
  49. 48.
    Dong Y, Ménage S, Brennan BA, Elgren TE, Jang HG, Pearce LL, Que L (1993) J Am Chem Soc 115: 1851CrossRefGoogle Scholar
  50. 49.
    Dong Y, Zang Y, Shu L, Wilkinson EC, Que L, Kauffmann K, Münck E (1997) J Am Chem Soc 119: 12,683Google Scholar
  51. 50. (a)
    Kitajima N, Fukui H, Moro-oka Y (1990) J Am Chem Soc 112: 6402CrossRefGoogle Scholar
  52. 59. (b)
    Kitajima N, Tamura N, Amagai H, Fukui H, Moro-Oka Y, Mizutani Y, Kitagawa T, Mathur R, Heerwegh K, Reed CA, Randall CR, Que L, Tatsumi K (1994) J Am Chem Soc 116: 9071CrossRefGoogle Scholar
  53. 51.
    Sawyer DT, McDowell MS, Spencer L, Tsang PKS (1989) Inorg Chem 28: 1166CrossRefGoogle Scholar
  54. 52.
    Ménage S, Brennan BA, Juarez-Garcia C, Münck E, Que L (1990) J Am Chem Soc 112: 6423CrossRefGoogle Scholar
  55. 53.
    Murch BP, Bradley FC, Que L (1986) J Am Chem Soc 108: 5027CrossRefGoogle Scholar
  56. 54.
    Hagadorn JR, Que L, Tolman WB (1998) J Am Chem Soc 120: 13,531CrossRefGoogle Scholar
  57. 55.
    Hayashi Y, Kayatani T, Sugimoto H, Suzuki M, Inomata K, Uehara A, Mizutani Y, Kitagawa T, Maeda Y (1995) J Am Chem Soc 117: 11,220Google Scholar
  58. 56.
    Herold S, Lippard SJ (1997) J Am Chem Soc 119: 145CrossRefGoogle Scholar
  59. 57.
    Kimura E, Kodama M, Machida R, Ishizu K (1982) Inorg Chem 21: 595CrossRefGoogle Scholar
  60. 58.
    Moënne-Loccoz P, Krebs C, Herlihy K, Edmonson, DE, Theil EC, Huynh BH, Loehr TM (1999) Biochemistry 38: 5290CrossRefGoogle Scholar
  61. 59.
    Moënne-Loccoz P, Baldwin J, Ley BA, Loehr TM, Bollinger JM (1998) Biochemistry 37: 14,659CrossRefGoogle Scholar
  62. 60.
    Broadwater JA, Ai J, Loehr TM, Sanders-Loehr J, Fox BG (1998) Biochemistry 37: 14,664CrossRefGoogle Scholar
  63. 61.
    Friant P, Goulon J, Fischer J, Ricard L, Schappacher M, Weiss R, Momenteau M (1985) Nouveau J Chimie 9: 33Google Scholar
  64. 62.
    Burstyn JN, Roe JA, Miksztal AR, Shaevitz BA, Lang G, Valentine JS (1988) J Am Chem Soc 110: 1382CrossRefGoogle Scholar
  65. 63.
    Shu L, Nesheim JC, Kauffmann K, Münck E, Lipscomb JD, Que L (1997) Science 275: 515CrossRefGoogle Scholar
  66. 64.
    Lee SY, Lipscomb JD (1999) Biochemistry 38: 4423CrossRefGoogle Scholar
  67. 65.
    Ho RYN, Roelfes G, Hermant R, Hage R, Feringa BL, Que L (1999) Chem Commun 2161Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2000

Authors and Affiliations

  • Jean-Jacques Girerd
    • 1
  • Frédéric Banse
    • 1
  • Ariane Jalila Simaan
    • 1
  1. 1.Laboratoire de Chimie Inorganique, UMR CNRS 8613Université Paris-SudOrsay cedexFrance

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