Selective oxidation of alkanes promoted by copper ions

Donald M. Camaioni; Michael A. Lilga; Timothy Bays Bays; John Linehan; Wendy J. Shaw; Jerome C. Birnbaum

Selective oxidation of alkanes promoted by copper ions

Donald M. Camaioni, Michael A. Lilga, Timothy Bays Bays, John Linehan, Wendy J. Shaw, Jerome C. Birnbaum

Pacific Northwest National Laboratory

Research output: Chapter in Book/Report/Conference proceeding › Chapter

Abstract

A system that uses the Cu(I)/Cu(II) couple and O₂ oxidizes alkanes, including methane, to alkyl ester in trifluoroacetic acid (TFA). Formation of an ester in large part protects the alkyl group from further oxidation, and the esters may then be hydrolyzed to the corresponding alcohol. We show that the system can be adapted to operate electrocatalytically with oxidation of alkane occuring in the cathodic compartment of an electrolysis cell due to the activation of O₂ by electrogcnerated Cu(I) ions. The mechanism of the oxidation appears to involve alkyl radicals. Trapping by Cu(II) ions converts the alkyl radicals to the ester product. Alkyl radicals with 2 or more carbons may first convert to olefins which subsequently add TFA to give ester products. The results are compared with oxidation of alkanes in Cu(II)-H₂O₂-TFA.

Original language	English
Title of host publication	ACS Division of Fuel Chemistry, Preprints
Pages	516-520
Number of pages	5
Volume	44
Edition	3
Publication status	Published - 1999

ASJC Scopus subject areas

Energy(all)

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Camaioni, D. M., Lilga, M. A., Bays, T. B., Linehan, J., Shaw, W. J., & Birnbaum, J. C. (1999). Selective oxidation of alkanes promoted by copper ions. In ACS Division of Fuel Chemistry, Preprints (3 ed., Vol. 44, pp. 516-520)

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abstract = "A system that uses the Cu(I)/Cu(II) couple and O2 oxidizes alkanes, including methane, to alkyl ester in trifluoroacetic acid (TFA). Formation of an ester in large part protects the alkyl group from further oxidation, and the esters may then be hydrolyzed to the corresponding alcohol. We show that the system can be adapted to operate electrocatalytically with oxidation of alkane occuring in the cathodic compartment of an electrolysis cell due to the activation of O2 by electrogcnerated Cu(I) ions. The mechanism of the oxidation appears to involve alkyl radicals. Trapping by Cu(II) ions converts the alkyl radicals to the ester product. Alkyl radicals with 2 or more carbons may first convert to olefins which subsequently add TFA to give ester products. The results are compared with oxidation of alkanes in Cu(II)-H2O2-TFA.",

author = "Camaioni, {Donald M.} and Lilga, {Michael A.} and Bays, {Timothy Bays} and John Linehan and Shaw, {Wendy J.} and Birnbaum, {Jerome C.}",

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T1 - Selective oxidation of alkanes promoted by copper ions

AU - Camaioni, Donald M.

AU - Lilga, Michael A.

AU - Bays, Timothy Bays

AU - Linehan, John

AU - Shaw, Wendy J.

AU - Birnbaum, Jerome C.

PY - 1999

Y1 - 1999

N2 - A system that uses the Cu(I)/Cu(II) couple and O2 oxidizes alkanes, including methane, to alkyl ester in trifluoroacetic acid (TFA). Formation of an ester in large part protects the alkyl group from further oxidation, and the esters may then be hydrolyzed to the corresponding alcohol. We show that the system can be adapted to operate electrocatalytically with oxidation of alkane occuring in the cathodic compartment of an electrolysis cell due to the activation of O2 by electrogcnerated Cu(I) ions. The mechanism of the oxidation appears to involve alkyl radicals. Trapping by Cu(II) ions converts the alkyl radicals to the ester product. Alkyl radicals with 2 or more carbons may first convert to olefins which subsequently add TFA to give ester products. The results are compared with oxidation of alkanes in Cu(II)-H2O2-TFA.

AB - A system that uses the Cu(I)/Cu(II) couple and O2 oxidizes alkanes, including methane, to alkyl ester in trifluoroacetic acid (TFA). Formation of an ester in large part protects the alkyl group from further oxidation, and the esters may then be hydrolyzed to the corresponding alcohol. We show that the system can be adapted to operate electrocatalytically with oxidation of alkane occuring in the cathodic compartment of an electrolysis cell due to the activation of O2 by electrogcnerated Cu(I) ions. The mechanism of the oxidation appears to involve alkyl radicals. Trapping by Cu(II) ions converts the alkyl radicals to the ester product. Alkyl radicals with 2 or more carbons may first convert to olefins which subsequently add TFA to give ester products. The results are compared with oxidation of alkanes in Cu(II)-H2O2-TFA.

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