Photooxidation of Methane to Methanol by Perrhenate in Water under Ambient Conditions

Kunkely, Horst; Vogler, Arnd

doi:10.5560/znb.2013-3104

Cited by 3 publications

(1 citation statement)

References 13 publications

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“…Turnovers (TOs) are attained for the conversion of light alkanes to tert -butoxycarbonyl-protected hydrazines using cerium chloride photocatalysts . The selective conversion of methane to methanol using a TiO 2 -supported Fe catalyst and hydrogen peroxide (H 2 O 2 ) as a terminal oxidant was reported, as well as aqueous photooxidation of methane to methanol with perrhenate salts . Previously, our groups have reported oxyesterification of light alkanes in trifluoroacetic acid (HTFA), in both thermal and photolytic processes, − and the group of Goldberg and Schelter have reported an aerobic photocatalytic process for alkane iodination…”

Section: Introductionmentioning

confidence: 99%

Aerobic Partial Oxidation of Alkanes Using Photodriven Iron Catalysis

et al. 2021

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Photodriven oxidations of alkanes in trifluoroacetic acid using commercial and synthesized Fe(III) sources as catalyst precursors and dioxygen (O2) as the terminal oxidant are reported. The reactions produce alkyl esters and occur at ambient temperature in the presence of air, and catalytic turnover is observed for the oxidation of methane in a pure O2 atmosphere. Under optimized conditions, approximately 17% conversion of methane to methyl trifluoroacetate at more than 50% selectivity is observed. It is demonstrated that methyl trifluoroacetate is stable under catalytic conditions, and thus overoxidized products are not formed through secondary oxidation of methyl trifluoroacetate.

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Section: Introductionmentioning

confidence: 99%

Aerobic Partial Oxidation of Alkanes Using Photodriven Iron Catalysis

et al. 2021

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Selective Photo‐Oxygenation of Light Alkanes Using Iodine Oxides and Chloride

et al. 2019

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Partial oxidation of light alkanes to generate alkyl esters has been achieved under photochemical conditions using mixtures of iodine oxides and chloride salts in trifluoroacetic acid (HTFA). The reactions are catalytic in chloride and are successful using compact fluorescent light, but higher yields are obtained using a mercury lamp. In this photo‐initiated oxyesterification process, the robust alkyl ester products are resistant to over‐oxidation, and under optimized conditions yields for alkyl ester production of ∼50 % based on methane, ∼60 % based on ethane (with a total functionalized yield of EtX (X=TFA or Cl) of 80 %) and ∼30 % based on propane have been demonstrated. The reaction also proceeds in aqueous HTFA and dichloroacetic acid with lower yields. Mechanistic studies indicate that the process likely operates by a chlorine hydrogen atom abstraction pathway wherein alkyl radicals are generated, trapped by iodine, and converted to alkyl trifluoroacetates in situ.

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