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Communication

Spectroscopic Characterization of a Hydroperoxo–Heme Intermediate: Conversion of a Side-On Peroxo to an End-On Hydroperoxo Complex†

  1. Jin-Gang Liu Dr.1,
  2. Takehiro Ohta Dr.1,
  3. Satoru Yamaguchi Dr.3,
  4. Takashi Ogura Prof. Dr.3,
  5. Satoshi Sakamoto2,
  6. Yonezo Maeda Prof. Dr.2,
  7. Yoshinori Naruta Prof. Dr.1

Article first published online: 30 OCT 2009

DOI: 10.1002/anie.200904572

Issue

Angewandte Chemie International Edition

Angewandte Chemie International Edition

Volume 48, Issue 49, pages 9262–9267, November 23, 2009

Additional Information

How to Cite

Liu, J.-G., Ohta, T., Yamaguchi, S., Ogura, T., Sakamoto, S., Maeda, Y. and Naruta, Y. (2009), Spectroscopic Characterization of a Hydroperoxo–Heme Intermediate: Conversion of a Side-On Peroxo to an End-On Hydroperoxo Complex. Angew. Chem. Int. Ed., 48: 9262–9267. doi: 10.1002/anie.200904572

Author Information

  1. 1

    Institute for Materials Chemistry and Engineering, Kyushu University, Higashi-ku, Fukuoka, 812-8581 (Japan), Fax: (+81) 92-642-2715 http//narutalab.ifoc.kyushu-u.ac.jp

  2. 2

    Graduate School of Sciences, Kyushu University, Higashi-ku, Fukuoka 812-8581 (Japan)

  3. 3

    Graduate School of Life Sciences, University of Hyogo, Hyogo, 678-1297 (Japan)

  1. †

    This work was financially supported by Grants-in-Aid for Scientific Research (S) (no. 17105003, YN), for Young Scientists (B) (no. 27150173, JGL) from JSPS, on Priority Areas (no. 19027044, YN), Innovative Areas (no. 20200050, JGL) from MEXT; and by the Elemental Science and Technology Project from MEXT. The 430 nm laser was set up by Dr. Ken’ichi Nakagawa, The University of Electro-Communications (Japan).

Publication History

  1. Issue published online: 17 NOV 2009
  2. Article first published online: 30 OCT 2009
  3. Manuscript Received: 17 AUG 2009

Funded by

  • JSPS
  • MEXT

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Keywords:

  • bioinorganic chemistry;
  • enzyme models;
  • heme proteins;
  • iron;
  • O[BOND]O activation
Thumbnail image of graphical abstract

Modeling job: Protonation of a closed seven-coordinate side-on heme peroxide can switch its spin state from high- to low-spin and convert the η2 binding fashion into a monodentate configuration to afford the corresponding hydroperoxide (see scheme). The end-on low-spin ferric hydroperoxo–heme species bear a covalently appended axial imidazole ligand and are easily prepared.

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