Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex

Chien Wei Chiang; Scott T. Kleespies; Heather D. Stout; Katlyn K. Meier; Po Yi Li; Emile L. Bominaar; Lawrence Que; Eckard Münck; Way Zen Lee

doi:10.1021/ja504410s

Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex

Chien Wei Chiang, Scott T. Kleespies, Heather D. Stout, Katlyn K. Meier, Po Yi Li, Emile L. Bominaar, Lawrence Que, Eckard Münck, Way Zen Lee

Chemistry (Twin Cities)

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Abstract

O₂ bubbling into a THF solution of Fe^II(BDPP) (1) at -80 °C generates a reversible bright yellow adduct 2. Characterization by resonance Raman and Mössbauer spectroscopy provides complementary insights into the nature of 2. The former shows a resonance-enhanced vibration at 1125 cm^-1, which can be assigned to the ν(O-O) of a bound superoxide, while the latter reveals the presence of a high-spin iron(III) center that is exchange-coupled to the superoxo ligand, like the Fe^III-O ₂^- pair found for the O₂ adduct of 4-nitrocatechol-bound homoprotocatechuate 2,3-dioxygenase. Lastly, 2 oxidizes dihydroanthracene to anthracene, supporting the notion that Fe ^III-O₂^- species can carry out H atom abstraction from a C-H bond to initiate the 4-electron oxidation of substrates proposed for some nonheme iron enzymes.

Original language	English (US)
Pages (from-to)	10846-10849
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	136
Issue number	31
DOIs	https://doi.org/10.1021/ja504410s
State	Published - Aug 6 2014

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title = "Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex",

abstract = "O2 bubbling into a THF solution of FeII(BDPP) (1) at -80 °C generates a reversible bright yellow adduct 2. Characterization by resonance Raman and M{\"o}ssbauer spectroscopy provides complementary insights into the nature of 2. The former shows a resonance-enhanced vibration at 1125 cm-1, which can be assigned to the ν(O-O) of a bound superoxide, while the latter reveals the presence of a high-spin iron(III) center that is exchange-coupled to the superoxo ligand, like the FeIII-O 2- pair found for the O2 adduct of 4-nitrocatechol-bound homoprotocatechuate 2,3-dioxygenase. Lastly, 2 oxidizes dihydroanthracene to anthracene, supporting the notion that Fe III-O2- species can carry out H atom abstraction from a C-H bond to initiate the 4-electron oxidation of substrates proposed for some nonheme iron enzymes.",

author = "Chiang, {Chien Wei} and Kleespies, {Scott T.} and Stout, {Heather D.} and Meier, {Katlyn K.} and Li, {Po Yi} and Bominaar, {Emile L.} and Lawrence Que and Eckard M{\"u}nck and Lee, {Way Zen}",

year = "2014",

month = aug,

day = "6",

doi = "10.1021/ja504410s",

language = "English (US)",

volume = "136",

pages = "10846--10849",

journal = "Journal of the American Chemical Society",

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T1 - Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex

AU - Chiang, Chien Wei

AU - Kleespies, Scott T.

AU - Stout, Heather D.

AU - Meier, Katlyn K.

AU - Li, Po Yi

AU - Bominaar, Emile L.

AU - Que, Lawrence

AU - Münck, Eckard

AU - Lee, Way Zen

PY - 2014/8/6

Y1 - 2014/8/6

N2 - O2 bubbling into a THF solution of FeII(BDPP) (1) at -80 °C generates a reversible bright yellow adduct 2. Characterization by resonance Raman and Mössbauer spectroscopy provides complementary insights into the nature of 2. The former shows a resonance-enhanced vibration at 1125 cm-1, which can be assigned to the ν(O-O) of a bound superoxide, while the latter reveals the presence of a high-spin iron(III) center that is exchange-coupled to the superoxo ligand, like the FeIII-O 2- pair found for the O2 adduct of 4-nitrocatechol-bound homoprotocatechuate 2,3-dioxygenase. Lastly, 2 oxidizes dihydroanthracene to anthracene, supporting the notion that Fe III-O2- species can carry out H atom abstraction from a C-H bond to initiate the 4-electron oxidation of substrates proposed for some nonheme iron enzymes.

AB - O2 bubbling into a THF solution of FeII(BDPP) (1) at -80 °C generates a reversible bright yellow adduct 2. Characterization by resonance Raman and Mössbauer spectroscopy provides complementary insights into the nature of 2. The former shows a resonance-enhanced vibration at 1125 cm-1, which can be assigned to the ν(O-O) of a bound superoxide, while the latter reveals the presence of a high-spin iron(III) center that is exchange-coupled to the superoxo ligand, like the FeIII-O 2- pair found for the O2 adduct of 4-nitrocatechol-bound homoprotocatechuate 2,3-dioxygenase. Lastly, 2 oxidizes dihydroanthracene to anthracene, supporting the notion that Fe III-O2- species can carry out H atom abstraction from a C-H bond to initiate the 4-electron oxidation of substrates proposed for some nonheme iron enzymes.

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JO - Journal of the American Chemical Society

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Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex

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