Catalytic carbon-carbon and carbon-hydrogen bond cleavage in lower alkanes. Low-temperature hydroxylations and hydroxycarbonylations with dioxygen as the oxidant

Minren Lin, Terrence E. Hogan, Ayusman Sen

Research output: Contribution to journalArticle

107 Citations (Scopus)

Abstract

RhCl3, in the presence of several equivalents of Cl- and I- ions, catalyzed the direct formation of methanol and acetic acid from methane, carbon monoxide, and dioxygen at 80-85°C in a 6:1 mixture of perfluorobutyric acid and water (approximate turnover rate: 2.9/h based on Rh). It was possible to selectively form either methanol or acetic acid by a simple change in the solvent system. As might be anticipated, ethane was more reactive than methane, and under similar reaction conditions formed methanol, ethanol, and acetic acid (approximate turnover rate: 7.5/h based on Rh). For both methane and ethane, the product alcohols were less reactive than the starting alkanes. Methyl iodide was also less reactive than methane. Most significantly, for ethane and higher alkanes products derived from C-C cleavage dominated over those derived from C-H cleavage on a per bond basis. Indeed, C-C cleavage products were virtually all that were observed with butane, isopentane, and 2,3-dimethylbutane. While the mechanism of the C-H and C-C cleavage steps remains to be elucidated, preliminary indications are that outer-sphere electron transfer or bond homolysis resulting in the formation of alkyl radicals did not occur.

Original languageEnglish (US)
Pages (from-to)4574-4580
Number of pages7
JournalJournal of the American Chemical Society
Volume118
Issue number19
DOIs
StatePublished - Jan 1 1996

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Hydroxylation
Alkanes
Methane
Oxidants
Paraffins
Ethane
Hydrogen
Hydrogen bonds
Carbon
Acetic acid
Acetic Acid
Oxygen
Methanol
Temperature
Butane
Carbon Monoxide
Carbon monoxide
Alcohols
Ethanol
Electrons

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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title = "Catalytic carbon-carbon and carbon-hydrogen bond cleavage in lower alkanes. Low-temperature hydroxylations and hydroxycarbonylations with dioxygen as the oxidant",
abstract = "RhCl3, in the presence of several equivalents of Cl- and I- ions, catalyzed the direct formation of methanol and acetic acid from methane, carbon monoxide, and dioxygen at 80-85°C in a 6:1 mixture of perfluorobutyric acid and water (approximate turnover rate: 2.9/h based on Rh). It was possible to selectively form either methanol or acetic acid by a simple change in the solvent system. As might be anticipated, ethane was more reactive than methane, and under similar reaction conditions formed methanol, ethanol, and acetic acid (approximate turnover rate: 7.5/h based on Rh). For both methane and ethane, the product alcohols were less reactive than the starting alkanes. Methyl iodide was also less reactive than methane. Most significantly, for ethane and higher alkanes products derived from C-C cleavage dominated over those derived from C-H cleavage on a per bond basis. Indeed, C-C cleavage products were virtually all that were observed with butane, isopentane, and 2,3-dimethylbutane. While the mechanism of the C-H and C-C cleavage steps remains to be elucidated, preliminary indications are that outer-sphere electron transfer or bond homolysis resulting in the formation of alkyl radicals did not occur.",
author = "Minren Lin and Hogan, {Terrence E.} and Ayusman Sen",
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T1 - Catalytic carbon-carbon and carbon-hydrogen bond cleavage in lower alkanes. Low-temperature hydroxylations and hydroxycarbonylations with dioxygen as the oxidant

AU - Lin, Minren

AU - Hogan, Terrence E.

AU - Sen, Ayusman

PY - 1996/1/1

Y1 - 1996/1/1

N2 - RhCl3, in the presence of several equivalents of Cl- and I- ions, catalyzed the direct formation of methanol and acetic acid from methane, carbon monoxide, and dioxygen at 80-85°C in a 6:1 mixture of perfluorobutyric acid and water (approximate turnover rate: 2.9/h based on Rh). It was possible to selectively form either methanol or acetic acid by a simple change in the solvent system. As might be anticipated, ethane was more reactive than methane, and under similar reaction conditions formed methanol, ethanol, and acetic acid (approximate turnover rate: 7.5/h based on Rh). For both methane and ethane, the product alcohols were less reactive than the starting alkanes. Methyl iodide was also less reactive than methane. Most significantly, for ethane and higher alkanes products derived from C-C cleavage dominated over those derived from C-H cleavage on a per bond basis. Indeed, C-C cleavage products were virtually all that were observed with butane, isopentane, and 2,3-dimethylbutane. While the mechanism of the C-H and C-C cleavage steps remains to be elucidated, preliminary indications are that outer-sphere electron transfer or bond homolysis resulting in the formation of alkyl radicals did not occur.

AB - RhCl3, in the presence of several equivalents of Cl- and I- ions, catalyzed the direct formation of methanol and acetic acid from methane, carbon monoxide, and dioxygen at 80-85°C in a 6:1 mixture of perfluorobutyric acid and water (approximate turnover rate: 2.9/h based on Rh). It was possible to selectively form either methanol or acetic acid by a simple change in the solvent system. As might be anticipated, ethane was more reactive than methane, and under similar reaction conditions formed methanol, ethanol, and acetic acid (approximate turnover rate: 7.5/h based on Rh). For both methane and ethane, the product alcohols were less reactive than the starting alkanes. Methyl iodide was also less reactive than methane. Most significantly, for ethane and higher alkanes products derived from C-C cleavage dominated over those derived from C-H cleavage on a per bond basis. Indeed, C-C cleavage products were virtually all that were observed with butane, isopentane, and 2,3-dimethylbutane. While the mechanism of the C-H and C-C cleavage steps remains to be elucidated, preliminary indications are that outer-sphere electron transfer or bond homolysis resulting in the formation of alkyl radicals did not occur.

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