Fe(TPA)-catalyzed alkane hydroxylation can be a metal-based oxidation

Jinheung Kim; Cheal Kim; Roger G. Harrison; Elizabeth C. Wilkinson; Lawrence Que

doi:10.1016/S1381-1169(96)00364-0

Fe(TPA)-catalyzed alkane hydroxylation can be a metal-based oxidation

Jinheung Kim, Cheal Kim, Roger G. Harrison, Elizabeth C. Wilkinson, Lawrence Que

Department of Chemistry & Nanoscience

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

25 Scopus citations

Abstract

The hydroxylation of cyclohexane by t-butyl hydroperoxide using [Fe₂O(TPA)₂(H₂O)₂]⁴⁺ (1, TPA=tris(2-pyridylmethyl)amine) as the catalyst has been investigated with the use of a syringe pump to control the concentration of the alkyl hydroperoxide. Unlike an alkoxy radical-based radical chain autoxidation mechanism, the reaction observed produces only alcohol (no ketone) with a deuterium kinetic isotope effect of 10, similar to heme catalyzed hydroxylations. An alkylperoxoiron(III) intermediate can be trapped at -40°C and characterized by a number of spectroscopic methods. A mechanistic scheme is proposed involving this intermediate which either serves as the precursor to the metal-based oxidant or oxidizes the substrate directly.

Original language	English
Pages (from-to)	83-89
Number of pages	7
Journal	Journal of Molecular Catalysis A: Chemical
Volume	117
Issue number	1-3
DOIs	https://doi.org/10.1016/S1381-1169(96)00364-0
State	Published - 14 Mar 1997

Bibliographical note

Funding Information:
This work was supported by funds from the National Institutes of Health (Grant No. GM-38767).

Keywords

Alkylperoxide intermediates
Nonheme iron complexes
Oxygen activation

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10.1016/S1381-1169(96)00364-0

Cite this

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title = "Fe(TPA)-catalyzed alkane hydroxylation can be a metal-based oxidation",

abstract = "The hydroxylation of cyclohexane by t-butyl hydroperoxide using [Fe2O(TPA)2(H2O)2]4+ (1, TPA=tris(2-pyridylmethyl)amine) as the catalyst has been investigated with the use of a syringe pump to control the concentration of the alkyl hydroperoxide. Unlike an alkoxy radical-based radical chain autoxidation mechanism, the reaction observed produces only alcohol (no ketone) with a deuterium kinetic isotope effect of 10, similar to heme catalyzed hydroxylations. An alkylperoxoiron(III) intermediate can be trapped at -40°C and characterized by a number of spectroscopic methods. A mechanistic scheme is proposed involving this intermediate which either serves as the precursor to the metal-based oxidant or oxidizes the substrate directly.",

keywords = "Alkylperoxide intermediates, Nonheme iron complexes, Oxygen activation",

author = "Jinheung Kim and Cheal Kim and Harrison, {Roger G.} and Wilkinson, {Elizabeth C.} and Lawrence Que",

note = "Funding Information: This work was supported by funds from the National Institutes of Health (Grant No. GM-38767).",

year = "1997",

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doi = "10.1016/S1381-1169(96)00364-0",

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T1 - Fe(TPA)-catalyzed alkane hydroxylation can be a metal-based oxidation

AU - Kim, Jinheung

AU - Kim, Cheal

AU - Harrison, Roger G.

AU - Wilkinson, Elizabeth C.

AU - Que, Lawrence

N1 - Funding Information: This work was supported by funds from the National Institutes of Health (Grant No. GM-38767).

PY - 1997/3/14

Y1 - 1997/3/14

N2 - The hydroxylation of cyclohexane by t-butyl hydroperoxide using [Fe2O(TPA)2(H2O)2]4+ (1, TPA=tris(2-pyridylmethyl)amine) as the catalyst has been investigated with the use of a syringe pump to control the concentration of the alkyl hydroperoxide. Unlike an alkoxy radical-based radical chain autoxidation mechanism, the reaction observed produces only alcohol (no ketone) with a deuterium kinetic isotope effect of 10, similar to heme catalyzed hydroxylations. An alkylperoxoiron(III) intermediate can be trapped at -40°C and characterized by a number of spectroscopic methods. A mechanistic scheme is proposed involving this intermediate which either serves as the precursor to the metal-based oxidant or oxidizes the substrate directly.

AB - The hydroxylation of cyclohexane by t-butyl hydroperoxide using [Fe2O(TPA)2(H2O)2]4+ (1, TPA=tris(2-pyridylmethyl)amine) as the catalyst has been investigated with the use of a syringe pump to control the concentration of the alkyl hydroperoxide. Unlike an alkoxy radical-based radical chain autoxidation mechanism, the reaction observed produces only alcohol (no ketone) with a deuterium kinetic isotope effect of 10, similar to heme catalyzed hydroxylations. An alkylperoxoiron(III) intermediate can be trapped at -40°C and characterized by a number of spectroscopic methods. A mechanistic scheme is proposed involving this intermediate which either serves as the precursor to the metal-based oxidant or oxidizes the substrate directly.

KW - Alkylperoxide intermediates

KW - Nonheme iron complexes

KW - Oxygen activation

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JO - Journal of Molecular Catalysis A: Chemical

JF - Journal of Molecular Catalysis A: Chemical

IS - 1-3

ER -

Fe(TPA)-catalyzed alkane hydroxylation can be a metal-based oxidation

Abstract

Bibliographical note

Keywords

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