Biomimetic oxidation studies. 11. Alkane functionalization in aqueous solution utilizing in situ formed [Fe2O(ν1-H2O) (ν1-OAc)(TPA)2]3+, as an MMO model precatalyst, embedded in surface-derivatized silica and contained in micelles

Karine Neimann, Ronny Neumann, Alain Rabion, Robert M. Buchanan, Richard H. Fish

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31 Citations (Scopus)

Abstract

The biomimetic, methane monooxygenase enzyme (MMO) precatalyst, [Fe 2O(ν1-H2O)(ν1-OAc)(TPA)2] 3+ (TPA) tris[(2-pyridyl)methyl]amine), 1, formed in situ at pH 4.2 from [Fe2O(μ-OAc)(TPA)2]3+, 2, was embedded in an amorphous silicate surface modified by a combination of hydrophilic poly(ethylene oxide) and hydrophobic poly(propylene oxide). The resulting catalytic assembly was found to be a biomimetic model for the MMO active site within a hydrophobic macroenvironment, allowing alkane functionalization with tert-butyl hydroperoxide (TBHP)/O2 in an aqueous reaction medium (pH 4.2). For example, cyclohexane was oxidized to a mixture of cyclohexanone, cyclohexanol, and cyclohexyl-tert-butyl peroxide, in a ratio of ∼3:1:2. The balance between poly- (ethylene oxide) and poly(propylene oxide), tethered on the silica surface, was crucial for maximizing the catalytic activity. The silica-based catalytic assembly showed reactivity somewhat higher in comparison to an aqueous micelle system utilizing the surfactant, cetyltrimethylammonium hydrogen sulfate at its critical micelle concentration, in which functionalization of cyclohexane with TBHP/O2 in the presence of 1 was also studied at pH 4.2 and was found to provide similar products: cyclohexanol, cyclohexanone, and cyclohexyl-tert-butyl peroxide, in a ratio of ∼2:3:1. Moreover, the mechanism for both the silica-based catalytic assembly and the aqueous micelle system was found to occur via the Haber-Weiss process, in which redox chemistry between 1 and TBHP provides both the t-BuO• and t-BuOO• radicals. The t-BuO• radical initiates the C-H functionalization reaction to form the carbon radical, followed by O2 trapping, to provide cyclohexyl hydroperoxide, which produces the cyclohexanol and cyclohexanone in the presence of 1, whereas the coupling product emanates from t-BuOO• and cyclohexyl radicals. A discussion concerning both approaches for alkane functionalization in water will be presented.

Original languageEnglish
Pages (from-to)3575-3580
Number of pages6
JournalInorganic Chemistry
Volume38
Issue number15
DOIs
Publication statusPublished - 1999

Fingerprint

methane monooxygenase
Cyclohexanols
tert-Butylhydroperoxide
Alkanes
biomimetics
Biomimetics
Micelles
Silicon Dioxide
alkanes
enzymes
micelles
methane
silicon dioxide
Polyethylene oxides
aqueous solutions
Oxidation
oxidation
propylene oxide
assembly
peroxides

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

@article{307de4e582f1411d8ae79918b27fd876,
title = "Biomimetic oxidation studies. 11. Alkane functionalization in aqueous solution utilizing in situ formed [Fe2O(ν1-H2O) (ν1-OAc)(TPA)2]3+, as an MMO model precatalyst, embedded in surface-derivatized silica and contained in micelles",
abstract = "The biomimetic, methane monooxygenase enzyme (MMO) precatalyst, [Fe 2O(ν1-H2O)(ν1-OAc)(TPA)2] 3+ (TPA) tris[(2-pyridyl)methyl]amine), 1, formed in situ at pH 4.2 from [Fe2O(μ-OAc)(TPA)2]3+, 2, was embedded in an amorphous silicate surface modified by a combination of hydrophilic poly(ethylene oxide) and hydrophobic poly(propylene oxide). The resulting catalytic assembly was found to be a biomimetic model for the MMO active site within a hydrophobic macroenvironment, allowing alkane functionalization with tert-butyl hydroperoxide (TBHP)/O2 in an aqueous reaction medium (pH 4.2). For example, cyclohexane was oxidized to a mixture of cyclohexanone, cyclohexanol, and cyclohexyl-tert-butyl peroxide, in a ratio of ∼3:1:2. The balance between poly- (ethylene oxide) and poly(propylene oxide), tethered on the silica surface, was crucial for maximizing the catalytic activity. The silica-based catalytic assembly showed reactivity somewhat higher in comparison to an aqueous micelle system utilizing the surfactant, cetyltrimethylammonium hydrogen sulfate at its critical micelle concentration, in which functionalization of cyclohexane with TBHP/O2 in the presence of 1 was also studied at pH 4.2 and was found to provide similar products: cyclohexanol, cyclohexanone, and cyclohexyl-tert-butyl peroxide, in a ratio of ∼2:3:1. Moreover, the mechanism for both the silica-based catalytic assembly and the aqueous micelle system was found to occur via the Haber-Weiss process, in which redox chemistry between 1 and TBHP provides both the t-BuO• and t-BuOO• radicals. The t-BuO• radical initiates the C-H functionalization reaction to form the carbon radical, followed by O2 trapping, to provide cyclohexyl hydroperoxide, which produces the cyclohexanol and cyclohexanone in the presence of 1, whereas the coupling product emanates from t-BuOO• and cyclohexyl radicals. A discussion concerning both approaches for alkane functionalization in water will be presented.",
author = "Karine Neimann and Ronny Neumann and Alain Rabion and Buchanan, {Robert M.} and Fish, {Richard H.}",
year = "1999",
doi = "10.1021/ic990155b",
language = "English",
volume = "38",
pages = "3575--3580",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
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TY - JOUR

T1 - Biomimetic oxidation studies. 11. Alkane functionalization in aqueous solution utilizing in situ formed [Fe2O(ν1-H2O) (ν1-OAc)(TPA)2]3+, as an MMO model precatalyst, embedded in surface-derivatized silica and contained in micelles

AU - Neimann, Karine

AU - Neumann, Ronny

AU - Rabion, Alain

AU - Buchanan, Robert M.

AU - Fish, Richard H.

PY - 1999

Y1 - 1999

N2 - The biomimetic, methane monooxygenase enzyme (MMO) precatalyst, [Fe 2O(ν1-H2O)(ν1-OAc)(TPA)2] 3+ (TPA) tris[(2-pyridyl)methyl]amine), 1, formed in situ at pH 4.2 from [Fe2O(μ-OAc)(TPA)2]3+, 2, was embedded in an amorphous silicate surface modified by a combination of hydrophilic poly(ethylene oxide) and hydrophobic poly(propylene oxide). The resulting catalytic assembly was found to be a biomimetic model for the MMO active site within a hydrophobic macroenvironment, allowing alkane functionalization with tert-butyl hydroperoxide (TBHP)/O2 in an aqueous reaction medium (pH 4.2). For example, cyclohexane was oxidized to a mixture of cyclohexanone, cyclohexanol, and cyclohexyl-tert-butyl peroxide, in a ratio of ∼3:1:2. The balance between poly- (ethylene oxide) and poly(propylene oxide), tethered on the silica surface, was crucial for maximizing the catalytic activity. The silica-based catalytic assembly showed reactivity somewhat higher in comparison to an aqueous micelle system utilizing the surfactant, cetyltrimethylammonium hydrogen sulfate at its critical micelle concentration, in which functionalization of cyclohexane with TBHP/O2 in the presence of 1 was also studied at pH 4.2 and was found to provide similar products: cyclohexanol, cyclohexanone, and cyclohexyl-tert-butyl peroxide, in a ratio of ∼2:3:1. Moreover, the mechanism for both the silica-based catalytic assembly and the aqueous micelle system was found to occur via the Haber-Weiss process, in which redox chemistry between 1 and TBHP provides both the t-BuO• and t-BuOO• radicals. The t-BuO• radical initiates the C-H functionalization reaction to form the carbon radical, followed by O2 trapping, to provide cyclohexyl hydroperoxide, which produces the cyclohexanol and cyclohexanone in the presence of 1, whereas the coupling product emanates from t-BuOO• and cyclohexyl radicals. A discussion concerning both approaches for alkane functionalization in water will be presented.

AB - The biomimetic, methane monooxygenase enzyme (MMO) precatalyst, [Fe 2O(ν1-H2O)(ν1-OAc)(TPA)2] 3+ (TPA) tris[(2-pyridyl)methyl]amine), 1, formed in situ at pH 4.2 from [Fe2O(μ-OAc)(TPA)2]3+, 2, was embedded in an amorphous silicate surface modified by a combination of hydrophilic poly(ethylene oxide) and hydrophobic poly(propylene oxide). The resulting catalytic assembly was found to be a biomimetic model for the MMO active site within a hydrophobic macroenvironment, allowing alkane functionalization with tert-butyl hydroperoxide (TBHP)/O2 in an aqueous reaction medium (pH 4.2). For example, cyclohexane was oxidized to a mixture of cyclohexanone, cyclohexanol, and cyclohexyl-tert-butyl peroxide, in a ratio of ∼3:1:2. The balance between poly- (ethylene oxide) and poly(propylene oxide), tethered on the silica surface, was crucial for maximizing the catalytic activity. The silica-based catalytic assembly showed reactivity somewhat higher in comparison to an aqueous micelle system utilizing the surfactant, cetyltrimethylammonium hydrogen sulfate at its critical micelle concentration, in which functionalization of cyclohexane with TBHP/O2 in the presence of 1 was also studied at pH 4.2 and was found to provide similar products: cyclohexanol, cyclohexanone, and cyclohexyl-tert-butyl peroxide, in a ratio of ∼2:3:1. Moreover, the mechanism for both the silica-based catalytic assembly and the aqueous micelle system was found to occur via the Haber-Weiss process, in which redox chemistry between 1 and TBHP provides both the t-BuO• and t-BuOO• radicals. The t-BuO• radical initiates the C-H functionalization reaction to form the carbon radical, followed by O2 trapping, to provide cyclohexyl hydroperoxide, which produces the cyclohexanol and cyclohexanone in the presence of 1, whereas the coupling product emanates from t-BuOO• and cyclohexyl radicals. A discussion concerning both approaches for alkane functionalization in water will be presented.

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