Oxidation of carbon monoxide cocatalyzed by palladium(0) and the H 5PV2Mo10O40 polyoxometalate probed by electron paramagnetic resonance and aerobic catalysis

Hila Goldberg, Llia Kaminker, Daniella Goldfarb, Ronny Neumann

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

The H5PV2Mo10O40 polyoxometalate and Pd/AI2O3 were used as co-catalysts under anaerobic conditions for the activation and oxidation of CO to CO 2 by an electron transfer-oxygen transfer mechanism. Upon anaerobic reduction of H5PV2Mo10O40 with CO in the presence of Pd(0) two paramagnetic species were observed and characterized by continuous wave electron paramagnetic resonance (CW-EPR) and hyperfine sublevel correlation (HYSCORE) spectroscopic measurements. Major species I (65-70%) is assigned to a species resembling a vanadyl cation that is supported on the polyoxometalate and showed a bonding interaction with 13CO. Minor species II (30-35%) is attributed to a reduced species where the vanadium(IV) atom is incorporated in the polyoxometalate framework but slightly distanced from the phosphate core. Under aerobic conditions, CO/O2, a nucleophilic oxidant was formed as elucidated by oxidation of thianthrene oxide as a probe substrate. Oxidation reactions performed on terminal alkenes such as 1-octene yielded a complicated mixture of products that was, however, clearly a result of alkene epoxidation followed by subsequent reactions of the intermediate epoxide. The significant competing reaction was a hydro-carbonylation reaction that yielded a ∼1:1 mixture of linear/branched carboxylic acids.

Original languageEnglish
Pages (from-to)7947-7952
Number of pages6
JournalInorganic Chemistry
Volume48
Issue number16
DOIs
Publication statusPublished - Aug 17 2009

Fingerprint

Palladium
Carbon Monoxide
carbon monoxide
Catalysis
catalysis
Paramagnetic resonance
palladium
electron paramagnetic resonance
Oxidation
oxidation
Alkenes
alkenes
Carbonylation
Vanadium
epoxidation
Vanadates
Epoxidation
epoxy compounds
Epoxy Compounds
Carboxylic Acids

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Oxidation of carbon monoxide cocatalyzed by palladium(0) and the H 5PV2Mo10O40 polyoxometalate probed by electron paramagnetic resonance and aerobic catalysis. / Goldberg, Hila; Kaminker, Llia; Goldfarb, Daniella; Neumann, Ronny.

In: Inorganic Chemistry, Vol. 48, No. 16, 17.08.2009, p. 7947-7952.

Research output: Contribution to journalArticle

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