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

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

96 Citations (Scopus)

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
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
Publication status	Published - 2014 Aug 6

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja504410s

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@article{83c8547834594eda8669ffc7aa311fd0,

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",

volume = "136",

pages = "10846--10849",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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TY - JOUR

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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DO - 10.1021/ja504410s

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AN - SCOPUS:84905674440

SN - 0002-7863

VL - 136

SP - 10846

EP - 10849

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 31

ER -

Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex

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CCDC 1020020: Experimental Crystal Structure Determination

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Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex

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CCDC 1020020: Experimental Crystal Structure Determination

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