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

doi:10.1021/ic001058h

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

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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 (λ_max = 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)Fe^III-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)Fe^III-O^•].

Original language	English
Pages (from-to)	616-618
Number of pages	3
Journal	Inorganic Chemistry
Volume	41
Issue number	4
DOIs	https://doi.org/10.1021/ic001058h
Publication status	Published - Feb 25 2002
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic001058h

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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",

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doi = "10.1021/ic001058h",

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volume = "41",

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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•].

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

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