Palladium-mediated aerobic oxidation of organic substrates: The role of metal versus hydrogen peroxide

Joseph E. Remias, Ayusman Sen

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

Palladium species catalyze the aerobic oxidation of a variety of organic substrates. The reoxidation of palladium(0) to palladium(II) by dioxygen, a necessary step in these catalytic oxidations, results in the simultaneous formation of free peroxide. However, the continued catalytic generation of peroxide requires the rereduction of palladium(II) to palladium(0). This can be achieved by alkenes and alcohols which are then converted to carbonyl compounds. In these cases, no sacrificial coreductant is necessary and the peroxide appears to play no significant part in the oxidation of these substrates. On the other hand, palladium(II) does not readily oxidize primary or aromatic C-H bonds thereby preventing its reduction by them. Thus, a sacrificial coreductant is required to reduce palladium(II), and carbon monoxide and dihydrogen can fulfill this role. The peroxide generated in these cases is subsequently used to effect the oxidation of the alkane and arene either by palladium(II) or by a second catalyst.

Original languageEnglish (US)
Pages (from-to)33-38
Number of pages6
JournalJournal of Molecular Catalysis A: Chemical
Volume189
Issue number1
DOIs
StatePublished - Oct 16 2002

Fingerprint

Palladium
hydrogen peroxide
Hydrogen peroxide
Hydrogen Peroxide
palladium
Metals
Oxidation
oxidation
Peroxides
peroxides
Substrates
metals
Carbonyl compounds
Alkanes
carbonyl compounds
Catalytic oxidation
Alkenes
Carbon Monoxide
Carbon monoxide
Paraffins

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Process Chemistry and Technology
  • Physical and Theoretical Chemistry

Cite this

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abstract = "Palladium species catalyze the aerobic oxidation of a variety of organic substrates. The reoxidation of palladium(0) to palladium(II) by dioxygen, a necessary step in these catalytic oxidations, results in the simultaneous formation of free peroxide. However, the continued catalytic generation of peroxide requires the rereduction of palladium(II) to palladium(0). This can be achieved by alkenes and alcohols which are then converted to carbonyl compounds. In these cases, no sacrificial coreductant is necessary and the peroxide appears to play no significant part in the oxidation of these substrates. On the other hand, palladium(II) does not readily oxidize primary or aromatic C-H bonds thereby preventing its reduction by them. Thus, a sacrificial coreductant is required to reduce palladium(II), and carbon monoxide and dihydrogen can fulfill this role. The peroxide generated in these cases is subsequently used to effect the oxidation of the alkane and arene either by palladium(II) or by a second catalyst.",
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Palladium-mediated aerobic oxidation of organic substrates : The role of metal versus hydrogen peroxide. / Remias, Joseph E.; Sen, Ayusman.

In: Journal of Molecular Catalysis A: Chemical, Vol. 189, No. 1, 16.10.2002, p. 33-38.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Palladium-mediated aerobic oxidation of organic substrates

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AU - Sen, Ayusman

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N2 - Palladium species catalyze the aerobic oxidation of a variety of organic substrates. The reoxidation of palladium(0) to palladium(II) by dioxygen, a necessary step in these catalytic oxidations, results in the simultaneous formation of free peroxide. However, the continued catalytic generation of peroxide requires the rereduction of palladium(II) to palladium(0). This can be achieved by alkenes and alcohols which are then converted to carbonyl compounds. In these cases, no sacrificial coreductant is necessary and the peroxide appears to play no significant part in the oxidation of these substrates. On the other hand, palladium(II) does not readily oxidize primary or aromatic C-H bonds thereby preventing its reduction by them. Thus, a sacrificial coreductant is required to reduce palladium(II), and carbon monoxide and dihydrogen can fulfill this role. The peroxide generated in these cases is subsequently used to effect the oxidation of the alkane and arene either by palladium(II) or by a second catalyst.

AB - Palladium species catalyze the aerobic oxidation of a variety of organic substrates. The reoxidation of palladium(0) to palladium(II) by dioxygen, a necessary step in these catalytic oxidations, results in the simultaneous formation of free peroxide. However, the continued catalytic generation of peroxide requires the rereduction of palladium(II) to palladium(0). This can be achieved by alkenes and alcohols which are then converted to carbonyl compounds. In these cases, no sacrificial coreductant is necessary and the peroxide appears to play no significant part in the oxidation of these substrates. On the other hand, palladium(II) does not readily oxidize primary or aromatic C-H bonds thereby preventing its reduction by them. Thus, a sacrificial coreductant is required to reduce palladium(II), and carbon monoxide and dihydrogen can fulfill this role. The peroxide generated in these cases is subsequently used to effect the oxidation of the alkane and arene either by palladium(II) or by a second catalyst.

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