Reactivity of hydroperoxide bound to a mononuclear non-heme iron site

Akira Wada, Seiji Ogo, Shigenori Nagatomo, Teizo Kitagawa, Yoshihito Watanabe, Koichiro Jitsukawa, Hideki Masuda

Research output: Contribution to journalArticle

79 Citations (Scopus)

Abstract

The first isolation and spectroscopic characterization of the mononuclear hydroperoxo-iron(III) complex [Fe(H2bppa)(OOH)]2+ (2) and the stoichiometric oxidation of substrates by the mononuclear iron-oxo intermediate generated by its decomposition have been described. The purple species 2 obtained from reaction of [Fe(H2bppa)(HCOO)](CIO4)2 with H2O2 in acetone at -50 °C gave characteristic UV-vis (λmax = 568 nm, ε = 1200 M-1 cm-1), ESR (g = 7.54, 5.78, and 4.25, S = 5/2), and ESI mass spectra (m/z 288.5 corresponding to the ion, [Fe(bppa)(OOH)]2+), which revealed that 2 is a high-spin mononuclear iron(III) complex with a hydroperoxide in an end-on fashion. The resonance Raman spectrum of 2 in d6-acetone revealed two intense bands at 621 and 830 cm-1, which shifted to 599 and 813 cm-1, respectively, when reacted with 18O-labeled H2O2, Reactions of the isolated (bppa)FeIII-OOH (2) with various substrates (single turnover oxidations) exhibited that the iron-oxo intermediate generated by decomposition of 2 is a nucleophilic species formulated as [(H2bppa)FeIII-O].

Original languageEnglish
Pages (from-to)616-618
Number of pages3
JournalInorganic Chemistry
Volume41
Issue number4
DOIs
Publication statusPublished - Feb 25 2002
Externally publishedYes

Fingerprint

Hydrogen Peroxide
Iron
reactivity
iron
Acetone
acetone
Decomposition
decomposition
Oxidation
oxidation
Substrates
mass spectra
Paramagnetic resonance
Raman scattering
isolation
Ions
Raman spectra
ions

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Wada, A., Ogo, S., Nagatomo, S., Kitagawa, T., Watanabe, Y., Jitsukawa, K., & Masuda, H. (2002). Reactivity of hydroperoxide bound to a mononuclear non-heme iron site. Inorganic Chemistry, 41(4), 616-618. https://doi.org/10.1021/ic001058h

Reactivity of hydroperoxide bound to a mononuclear non-heme iron site. / Wada, Akira; Ogo, Seiji; Nagatomo, Shigenori; Kitagawa, Teizo; Watanabe, Yoshihito; Jitsukawa, Koichiro; Masuda, Hideki.

In: Inorganic Chemistry, Vol. 41, No. 4, 25.02.2002, p. 616-618.

Research output: Contribution to journalArticle

Wada, A, Ogo, S, Nagatomo, S, Kitagawa, T, Watanabe, Y, Jitsukawa, K & Masuda, H 2002, 'Reactivity of hydroperoxide bound to a mononuclear non-heme iron site', Inorganic Chemistry, vol. 41, no. 4, pp. 616-618. https://doi.org/10.1021/ic001058h
Wada A, Ogo S, Nagatomo S, Kitagawa T, Watanabe Y, Jitsukawa K et al. Reactivity of hydroperoxide bound to a mononuclear non-heme iron site. Inorganic Chemistry. 2002 Feb 25;41(4):616-618. https://doi.org/10.1021/ic001058h
Wada, Akira ; Ogo, Seiji ; Nagatomo, Shigenori ; Kitagawa, Teizo ; Watanabe, Yoshihito ; Jitsukawa, Koichiro ; Masuda, Hideki. / Reactivity of hydroperoxide bound to a mononuclear non-heme iron site. In: Inorganic Chemistry. 2002 ; Vol. 41, No. 4. pp. 616-618.
@article{7bdabc1fb19a419f862297f10f20ba90,
title = "Reactivity of hydroperoxide bound to a mononuclear non-heme iron site",
abstract = "The first isolation and spectroscopic characterization of the mononuclear hydroperoxo-iron(III) complex [Fe(H2bppa)(OOH)]2+ (2) and the stoichiometric oxidation of substrates by the mononuclear iron-oxo intermediate generated by its decomposition have been described. The purple species 2 obtained from reaction of [Fe(H2bppa)(HCOO)](CIO4)2 with H2O2 in acetone at -50 °C gave characteristic UV-vis (λmax = 568 nm, ε = 1200 M-1 cm-1), ESR (g = 7.54, 5.78, and 4.25, S = 5/2), and ESI mass spectra (m/z 288.5 corresponding to the ion, [Fe(bppa)(OOH)]2+), which revealed that 2 is a high-spin mononuclear iron(III) complex with a hydroperoxide in an end-on fashion. The resonance Raman spectrum of 2 in d6-acetone revealed two intense bands at 621 and 830 cm-1, which shifted to 599 and 813 cm-1, respectively, when reacted with 18O-labeled H2O2, Reactions of the isolated (bppa)FeIII-OOH (2) with various substrates (single turnover oxidations) exhibited that the iron-oxo intermediate generated by decomposition of 2 is a nucleophilic species formulated as [(H2bppa)FeIII-O•].",
author = "Akira Wada and Seiji Ogo and Shigenori Nagatomo and Teizo Kitagawa and Yoshihito Watanabe and Koichiro Jitsukawa and Hideki Masuda",
year = "2002",
month = "2",
day = "25",
doi = "10.1021/ic001058h",
language = "English",
volume = "41",
pages = "616--618",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "4",

}

TY - JOUR

T1 - Reactivity of hydroperoxide bound to a mononuclear non-heme iron site

AU - Wada, Akira

AU - Ogo, Seiji

AU - Nagatomo, Shigenori

AU - Kitagawa, Teizo

AU - Watanabe, Yoshihito

AU - Jitsukawa, Koichiro

AU - Masuda, Hideki

PY - 2002/2/25

Y1 - 2002/2/25

N2 - The first isolation and spectroscopic characterization of the mononuclear hydroperoxo-iron(III) complex [Fe(H2bppa)(OOH)]2+ (2) and the stoichiometric oxidation of substrates by the mononuclear iron-oxo intermediate generated by its decomposition have been described. The purple species 2 obtained from reaction of [Fe(H2bppa)(HCOO)](CIO4)2 with H2O2 in acetone at -50 °C gave characteristic UV-vis (λmax = 568 nm, ε = 1200 M-1 cm-1), ESR (g = 7.54, 5.78, and 4.25, S = 5/2), and ESI mass spectra (m/z 288.5 corresponding to the ion, [Fe(bppa)(OOH)]2+), which revealed that 2 is a high-spin mononuclear iron(III) complex with a hydroperoxide in an end-on fashion. The resonance Raman spectrum of 2 in d6-acetone revealed two intense bands at 621 and 830 cm-1, which shifted to 599 and 813 cm-1, respectively, when reacted with 18O-labeled H2O2, Reactions of the isolated (bppa)FeIII-OOH (2) with various substrates (single turnover oxidations) exhibited that the iron-oxo intermediate generated by decomposition of 2 is a nucleophilic species formulated as [(H2bppa)FeIII-O•].

AB - The first isolation and spectroscopic characterization of the mononuclear hydroperoxo-iron(III) complex [Fe(H2bppa)(OOH)]2+ (2) and the stoichiometric oxidation of substrates by the mononuclear iron-oxo intermediate generated by its decomposition have been described. The purple species 2 obtained from reaction of [Fe(H2bppa)(HCOO)](CIO4)2 with H2O2 in acetone at -50 °C gave characteristic UV-vis (λmax = 568 nm, ε = 1200 M-1 cm-1), ESR (g = 7.54, 5.78, and 4.25, S = 5/2), and ESI mass spectra (m/z 288.5 corresponding to the ion, [Fe(bppa)(OOH)]2+), which revealed that 2 is a high-spin mononuclear iron(III) complex with a hydroperoxide in an end-on fashion. The resonance Raman spectrum of 2 in d6-acetone revealed two intense bands at 621 and 830 cm-1, which shifted to 599 and 813 cm-1, respectively, when reacted with 18O-labeled H2O2, Reactions of the isolated (bppa)FeIII-OOH (2) with various substrates (single turnover oxidations) exhibited that the iron-oxo intermediate generated by decomposition of 2 is a nucleophilic species formulated as [(H2bppa)FeIII-O•].

UR - http://www.scopus.com/inward/record.url?scp=0037169656&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0037169656&partnerID=8YFLogxK

U2 - 10.1021/ic001058h

DO - 10.1021/ic001058h

M3 - Article

C2 - 11849054

AN - SCOPUS:0037169656

VL - 41

SP - 616

EP - 618

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 4

ER -