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
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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 -