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

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

Keywords

Alkylperoxide intermediates
Nonheme iron complexes
Oxygen activation

Access to Document

10.1016/S1381-1169(96)00364-0

Cite this

@article{afb2ea18c09e40629310e0e29aa8f0fa,

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",

month = mar,

day = "14",

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

language = "English",

volume = "117",

pages = "83--89",

journal = "Journal of Molecular Catalysis A: Chemical",

issn = "1381-1169",

publisher = "Elsevier BV",

number = "1-3",

}

TY - JOUR

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

UR - http://www.scopus.com/inward/record.url?scp=0030910764&partnerID=8YFLogxK

U2 - 10.1016/S1381-1169(96)00364-0

DO - 10.1016/S1381-1169(96)00364-0

M3 - Article

AN - SCOPUS:0030910764

SN - 1381-1169

VL - 117

SP - 83

EP - 89

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

Keywords

Access to Document

Fingerprint

Cite this