Cobalt‐Catalyzed Oxidation of Methane to Methyl Trifluoroacetate by Dioxygen

Straßner, Thomas; Ahrens, Sebastian; Muehlhofer, Michael; Munz, Dominik; Zeller, Alexander

doi:10.1002/ejic.201300213

Cited by 52 publications

(43 citation statements)

References 80 publications

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“…During the past several decades, many metals have been studied in catalytic activation and functionalization of carbon-hydrogen bonds. The reader is directed to selected recent examples with gold [123], cobalt [124][125][126] chromium [127], copper [128][129][130][131] iron [132][133][134][135], iridium [136], manganese [137][138][139], molybdenum [140], nickel [141], osmium [142][143][144][145][146][147][148], palladium [149][150][151], rhenium [152], rhodium [153,154], ruthenium [155,156], and vanadium [157,158].…”

Section: Metal Ions Most Active In Oxidation Catalysismentioning

confidence: 99%

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

Shul’pin

2016

Catalysts

173

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This review describes new reactions catalyzed by recently discovered types of metal complexes and catalytic systems (catalyst + co-catalyst). Works of recent years (mainly 2010-2016) devoted to the oxygenations of saturated, aromatic hydrocarbons and other carbon-hydrogen compounds are surveyed. Both soluble metal complexes and solid metal compounds catalyze such transformations. Molecular oxygen, hydrogen peroxide, alkyl peroxides, and peroxy acids were used in these reactions as oxidants.

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Section: Metal Ions Most Active In Oxidation Catalysismentioning

confidence: 99%

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

Shul’pin

2016

Catalysts

173

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“…The NHC complexes were very resistant under the acidic conditions required for methane C−H activation. Methyl trifluoroacetate yields of 37 and 50 % were reported with manganese oxide and cobalt acetate, respectively, as catalysts in a mixture of trifluoroacetic acid and trifluoroacetic anhydride. The stoichiometry of methane oxidation to methyl trifluoroacetate with potassium persulfate as the oxidant is as follows [Eq.…”

Section: Catalytic Results Of Copper‐based Homogenous Catalysts For Tmentioning

confidence: 99%

Homogeneous Copper‐Catalyzed Conversion of Methane to Methyl Trifluoroacetate in High Yield at Low Pressure

Ravi

Bokhoven

2018

ChemCatChem

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The direct catalytic oxidation of methane to oxygenates, a reaction that garners significant scientific and industrial interest, is plagued by poor methane‐based yields. Some of the best homogeneous catalytic systems reported to date convert methane to methyl esters using catalysts with complex organic ligands to reach high yields at relatively high temperature (>423 K) and pressure (20–70 bar). In our study, we used a simple copper compound, copper(II) oxide, to selectively convert methane to methyl trifluoroacetate at 363 K and low pressure (5 bar) resulting in yields as high as 63 % at a methane conversion of 71 %. The catalyst is easily recovered by treating the spent reaction mixture with a base, and the catalytic performance of the recovered material is highly comparable to that of the fresh catalyst. In terms of turnover, copper oxide (TON=33 for ester yield of 56 %) ranks higher than other simple metal compounds and is comparable to catalysts with NHC ligands. Thus, this work demonstrates the possibility of using a simple catalyst devoid of complex ligands to convert methane in high yields at low pressure.

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“…[6, 9j, 16] Indeed, this strategy for product protection is also applicable to radicals, which are by nature electron deficient. [17] Product protection studies were carried out for the Rh(bisq x ) family of rhodium-ligand complexes. The results are summarized in Figure 3.…”

Section: Discussionmentioning

confidence: 99%

Rhodium Bis(quinolinyl)benzene Complexes for Methane Activation and Functionalization

O’Reilly

Nielsen

et al. 2014

Chemistry A European J

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A series of rhodium(III) bis(quinolinyl)benzene (bisqx) complexes was studied as candidates for the homogeneous partial oxidation of methane. Density functional theory (DFT) (M06 with Poisson continuum solvation) was used to investigate a variety of (bisqx) ligand candidates involving different functional groups to determine the impact on RhIII(bisqx)‐catalyzed methane functionalization. The free energy activation barriers for methane CH activation and Rh–methyl functionalization at 298 K and 498 K were determined. DFT studies predict that the best candidate for catalytic methane functionalization is RhIII coordinated to unsubstituted bis(quinolinyl)benzene (bisq). Support is also found for the prediction that the η2‐benzene coordination mode of (bisqx) ligands on Rh encourages methyl group functionalization by serving as an effective leaving group for SN2 and SR2 attack.

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Cobalt‐Catalyzed Oxidation of Methane to Methyl Trifluoroacetate by Dioxygen

Abstract: The cobalt-catalyzed oxidation of methane to methyl trifluoroacetate by molecular oxygen in trifluoroacetic acid has been studied in detail. Yields of up to 50 % based on methane were obtained. The catalytic activities were highly depend-[a] Physikalische

Cited by 52 publications

References 80 publications

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

Homogeneous Copper‐Catalyzed Conversion of Methane to Methyl Trifluoroacetate in High Yield at Low Pressure

Rhodium Bis(quinolinyl)benzene Complexes for Methane Activation and Functionalization

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