Selective Monooxidation of Light Alkanes Using Chloride and Iodate

Fortman, George C.; Boaz, Nicholas C.; Munz, Dominik; Konnick, Michael M.; Periana, Roy A.; Groves, John T.; Gunnoe, T. Brent

doi:10.1021/ja502657g

Selective Monooxidation of Light Alkanes Using Chloride and Iodate

Journal Article · Wed May 28 00:00:00 EDT 2014 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja502657g· OSTI ID:1607836

Fortman, George C. ^[1]; Boaz, Nicholas C. ^[2]; Munz, Dominik ^[3]; Konnick, Michael M. ^[4]; Periana, Roy A. ^[4]; Groves, John T. ^[2]; Gunnoe, T. Brent ^[3]

Univ. of Virginia, Charlottesville, VA (United States); University of Virginia
Princeton Univ., NJ (United States)
Univ. of Virginia, Charlottesville, VA (United States)
Scripps Research Inst., Jupiter, FL (United States)

We describe here an efficient system for the direct partial oxidation of methane, ethane, and propane using iodate salts with catalytic amounts of chloride in protic solvents. In HTFA (TFA = trifluoroacetate), >20% methane conversion with >85% selectivity for MeTFA have been achieved. The addition of substoichiometric amounts of chloride is essential, and for methane the conversion increases from <1% in the absence of chloride to >20%. The reaction further proceeds in aqueous HTFA as well as acetic acid to afford methyl acetate. ¹³C labeling experiments showed that less than 2% of methane is overoxidized to ¹³CO₂ at 15% conversion of ¹³CH₄. The system is selective for higher alkanes: 30% ethane conversion with 98% selectivity for EtTFA and 19% propane conversion that is selective for mixtures of the mono- and difunctionalized TFA esters. Research of methane conversion using a series of iodine-based reagents [I₂, ICl, ICl₃, I(TFA)₃, I₂O₄, I₂O₅, (IO₂)₂S₂O₇, (IO)₂SO₄] indicated that the chloride enhancement is not limited to iodate

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Virginia, Charlottesville, VA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0001298

OSTI ID:: 1607836

Alternate ID(s):: OSTI ID: 1167704
OSTI ID: 1383900

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 23 Vol. 136; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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