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 |
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ASJC Scopus subject areas
- Energy(all)
Cite this
Selective oxidation of alkanes promoted by copper ions. / Camaioni, Donald M.; Lilga, Michael A.; Bays, Timothy Bays; Linehan, John; Shaw, Wendy J.; Birnbaum, Jerome C.
ACS Division of Fuel Chemistry, Preprints. Vol. 44 3. ed. 1999. p. 516-520.Research output: Chapter in Book/Report/Conference proceeding › Chapter
}
TY - CHAP
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.
UR - http://www.scopus.com/inward/record.url?scp=0032804850&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0032804850&partnerID=8YFLogxK
M3 - Chapter
VL - 44
SP - 516
EP - 520
BT - ACS Division of Fuel Chemistry, Preprints
ER -