Iron-oxidation-state-dependent O-O bond cleavage of meta-chloroperbenzoic acid to form an iron(IV)-oxo complex

Kallol Ray; Sang Mok Lee; Lawrence Que

doi:10.1016/j.ica.2007.07.039

Iron-oxidation-state-dependent O-O bond cleavage of meta-chloroperbenzoic acid to form an iron(IV)-oxo complex

Kallol Ray, Sang Mok Lee, Lawrence Que

Chemistry (Twin Cities)

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

26 Scopus citations

Abstract

The mechanism of formation of [Fe^IV(O)(N4Py)]²⁺ (2, N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) from the reaction of [Fe^II(N4Py)(CH₃CN)]²⁺ (1) with m-chloroperbenzoic acid (mCPBA) in CH₂Cl₂ at -30 °C has been studied on the basis of the visible spectral changes observed and the reaction stoichiometry. It is shown that the conversion of 1 to 2 in 90% yield requires 1.5 equiv. peracid and takes place in two successive one-electron steps via an [Fe^III(N4Py)OH]²⁺(3) intermediate. The first oxidation step uses 0.5 equiv. peracid and produces 0.5 equiv. 3-chlorobenzoic acid, while the second step uses 1 equiv. peracid and affords byproducts derived from chlorophenyl radical. We conclude that the Fe^II(N4Py) center promotes O-O bond heterolysis, while the Fe^III(N4Py) center favors O-O bond homolysis, so the nature of O-O bond cleavage is dependent on the iron oxidation state.

Original language	English (US)
Pages (from-to)	1066-1069
Number of pages	4
Journal	Inorganica Chimica Acta
Volume	361
Issue number	4
DOIs	https://doi.org/10.1016/j.ica.2007.07.039
State	Published - Mar 3 2008

Bibliographical note

Funding Information:
This work was supported by the National Institutes of Health (Grant GM-33162).

Keywords

Iron oxidation state
Non-heme ligands
O-O bond lysis
Oxoiron(IV) complexes

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10.1016/j.ica.2007.07.039

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title = "Iron-oxidation-state-dependent O-O bond cleavage of meta-chloroperbenzoic acid to form an iron(IV)-oxo complex",

abstract = "The mechanism of formation of [FeIV(O)(N4Py)]2+ (2, N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) from the reaction of [FeII(N4Py)(CH3CN)]2+ (1) with m-chloroperbenzoic acid (mCPBA) in CH2Cl2 at -30 °C has been studied on the basis of the visible spectral changes observed and the reaction stoichiometry. It is shown that the conversion of 1 to 2 in 90% yield requires 1.5 equiv. peracid and takes place in two successive one-electron steps via an [FeIII(N4Py)OH]2+(3) intermediate. The first oxidation step uses 0.5 equiv. peracid and produces 0.5 equiv. 3-chlorobenzoic acid, while the second step uses 1 equiv. peracid and affords byproducts derived from chlorophenyl radical. We conclude that the FeII(N4Py) center promotes O-O bond heterolysis, while the FeIII(N4Py) center favors O-O bond homolysis, so the nature of O-O bond cleavage is dependent on the iron oxidation state.",

keywords = "Iron oxidation state, Non-heme ligands, O-O bond lysis, Oxoiron(IV) complexes",

author = "Kallol Ray and Lee, {Sang Mok} and Lawrence Que",

note = "Funding Information: This work was supported by the National Institutes of Health (Grant GM-33162).",

year = "2008",

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doi = "10.1016/j.ica.2007.07.039",

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T1 - Iron-oxidation-state-dependent O-O bond cleavage of meta-chloroperbenzoic acid to form an iron(IV)-oxo complex

AU - Ray, Kallol

AU - Lee, Sang Mok

AU - Que, Lawrence

N1 - Funding Information: This work was supported by the National Institutes of Health (Grant GM-33162).

PY - 2008/3/3

Y1 - 2008/3/3

N2 - The mechanism of formation of [FeIV(O)(N4Py)]2+ (2, N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) from the reaction of [FeII(N4Py)(CH3CN)]2+ (1) with m-chloroperbenzoic acid (mCPBA) in CH2Cl2 at -30 °C has been studied on the basis of the visible spectral changes observed and the reaction stoichiometry. It is shown that the conversion of 1 to 2 in 90% yield requires 1.5 equiv. peracid and takes place in two successive one-electron steps via an [FeIII(N4Py)OH]2+(3) intermediate. The first oxidation step uses 0.5 equiv. peracid and produces 0.5 equiv. 3-chlorobenzoic acid, while the second step uses 1 equiv. peracid and affords byproducts derived from chlorophenyl radical. We conclude that the FeII(N4Py) center promotes O-O bond heterolysis, while the FeIII(N4Py) center favors O-O bond homolysis, so the nature of O-O bond cleavage is dependent on the iron oxidation state.

AB - The mechanism of formation of [FeIV(O)(N4Py)]2+ (2, N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) from the reaction of [FeII(N4Py)(CH3CN)]2+ (1) with m-chloroperbenzoic acid (mCPBA) in CH2Cl2 at -30 °C has been studied on the basis of the visible spectral changes observed and the reaction stoichiometry. It is shown that the conversion of 1 to 2 in 90% yield requires 1.5 equiv. peracid and takes place in two successive one-electron steps via an [FeIII(N4Py)OH]2+(3) intermediate. The first oxidation step uses 0.5 equiv. peracid and produces 0.5 equiv. 3-chlorobenzoic acid, while the second step uses 1 equiv. peracid and affords byproducts derived from chlorophenyl radical. We conclude that the FeII(N4Py) center promotes O-O bond heterolysis, while the FeIII(N4Py) center favors O-O bond homolysis, so the nature of O-O bond cleavage is dependent on the iron oxidation state.

KW - Iron oxidation state

KW - Non-heme ligands

KW - O-O bond lysis

KW - Oxoiron(IV) complexes

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ER -

Iron-oxidation-state-dependent O-O bond cleavage of meta-chloroperbenzoic acid to form an iron(IV)-oxo complex

Abstract

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