Conflicting Role of Water in the Activation of H2O2 and the Formation and Reactivity of Non-Heme FeIII-OOH and FeIII-O-FeIII Complexes at Room Temperature

Sandeep K. Padamati; Apparao Draksharapu; Duenpen Unjaroen; Wesley R. Browne

doi:10.1021/acs.inorgchem.5b02976

Conflicting Role of Water in the Activation of H₂O₂ and the Formation and Reactivity of Non-Heme Fe^III-OOH and Fe^III-O-Fe^III Complexes at Room Temperature

Sandeep K. Padamati, Apparao Draksharapu, Duenpen Unjaroen, Wesley R. Browne

Chemistry (Twin Cities)

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

13 Scopus citations

Abstract

The formation of an Fe^III-OOH species by reaction of complex 1 ([(MeN3Py)Fe^II(CH₃CN)₂]²⁺) with H₂O₂ at room temperature is reported and is studied by a combination of UV/vis absorption, EPR, and resonance Raman spectroscopies. The formation of the Fe^III-OOH species, and its subsequent conversion to relatively inert Fe^III-O-Fe^III species, is shown to be highly dependent on the concentration of water, with excess water favoring the formation of the latter species, which is studied by UV/vis absorption spectroelectrochemistry also. The presence of acetic acid increases the rate and extent of oxidation of 1 to its iron(III) state and inhibits the wasteful decomposition of H₂O₂ but does not affect significantly the spectroscopic properties of the Fe^III-OOH species formed.

Original language	English (US)
Pages (from-to)	4211-4222
Number of pages	12
Journal	Inorganic chemistry
Volume	55
Issue number	9
DOIs	https://doi.org/10.1021/acs.inorgchem.5b02976
State	Published - May 2 2016

Bibliographical note

Funding Information:
Financial support comes from the European Research Council (ERC-2011-StG-279549, WRB), The Netherlands Fund for Technology and Science STW (11059, WRB), the Ministry of Education, Culture and Science (Gravity program 024.001.035, AD, WRB), and the Ubbo Emmius Fund of the University of Groningen (AD). The COST action CM1305 Explicit control over spin-states in technology and biochemistry is acknowledged for discussion.

Publisher Copyright:
© 2016 American Chemical Society.

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10.1021/acs.inorgchem.5b02976

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title = "Conflicting Role of Water in the Activation of H2O2 and the Formation and Reactivity of Non-Heme FeIII-OOH and FeIII-O-FeIII Complexes at Room Temperature",

abstract = "The formation of an FeIII-OOH species by reaction of complex 1 ([(MeN3Py)FeII(CH3CN)2]2+) with H2O2 at room temperature is reported and is studied by a combination of UV/vis absorption, EPR, and resonance Raman spectroscopies. The formation of the FeIII-OOH species, and its subsequent conversion to relatively inert FeIII-O-FeIII species, is shown to be highly dependent on the concentration of water, with excess water favoring the formation of the latter species, which is studied by UV/vis absorption spectroelectrochemistry also. The presence of acetic acid increases the rate and extent of oxidation of 1 to its iron(III) state and inhibits the wasteful decomposition of H2O2 but does not affect significantly the spectroscopic properties of the FeIII-OOH species formed.",

author = "Padamati, {Sandeep K.} and Apparao Draksharapu and Duenpen Unjaroen and Browne, {Wesley R.}",

note = "Funding Information: Financial support comes from the European Research Council (ERC-2011-StG-279549, WRB), The Netherlands Fund for Technology and Science STW (11059, WRB), the Ministry of Education, Culture and Science (Gravity program 024.001.035, AD, WRB), and the Ubbo Emmius Fund of the University of Groningen (AD). The COST action CM1305 Explicit control over spin-states in technology and biochemistry is acknowledged for discussion. Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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AU - Padamati, Sandeep K.

AU - Draksharapu, Apparao

AU - Unjaroen, Duenpen

AU - Browne, Wesley R.

N1 - Funding Information: Financial support comes from the European Research Council (ERC-2011-StG-279549, WRB), The Netherlands Fund for Technology and Science STW (11059, WRB), the Ministry of Education, Culture and Science (Gravity program 024.001.035, AD, WRB), and the Ubbo Emmius Fund of the University of Groningen (AD). The COST action CM1305 Explicit control over spin-states in technology and biochemistry is acknowledged for discussion. Publisher Copyright: © 2016 American Chemical Society.

PY - 2016/5/2

Y1 - 2016/5/2

N2 - The formation of an FeIII-OOH species by reaction of complex 1 ([(MeN3Py)FeII(CH3CN)2]2+) with H2O2 at room temperature is reported and is studied by a combination of UV/vis absorption, EPR, and resonance Raman spectroscopies. The formation of the FeIII-OOH species, and its subsequent conversion to relatively inert FeIII-O-FeIII species, is shown to be highly dependent on the concentration of water, with excess water favoring the formation of the latter species, which is studied by UV/vis absorption spectroelectrochemistry also. The presence of acetic acid increases the rate and extent of oxidation of 1 to its iron(III) state and inhibits the wasteful decomposition of H2O2 but does not affect significantly the spectroscopic properties of the FeIII-OOH species formed.

AB - The formation of an FeIII-OOH species by reaction of complex 1 ([(MeN3Py)FeII(CH3CN)2]2+) with H2O2 at room temperature is reported and is studied by a combination of UV/vis absorption, EPR, and resonance Raman spectroscopies. The formation of the FeIII-OOH species, and its subsequent conversion to relatively inert FeIII-O-FeIII species, is shown to be highly dependent on the concentration of water, with excess water favoring the formation of the latter species, which is studied by UV/vis absorption spectroelectrochemistry also. The presence of acetic acid increases the rate and extent of oxidation of 1 to its iron(III) state and inhibits the wasteful decomposition of H2O2 but does not affect significantly the spectroscopic properties of the FeIII-OOH species formed.

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