The mechanism of propylene oxidation to acrolein over bismuth molybdate, copper oxide, and rhodium catalysts

M. Imachi, R. L. Kuczkowski, J. T. Groves, N. W. Cant

Research output: Contribution to journalArticle

21 Scopus citations

Abstract

The oxidation of (E)-propene-1-d1 to acrolein over bismuth molybdate, copper oxide, and rhodium catalysts was studied to determine if the reaction proceeded with (Z)-(E) randomization of the deuterium stereochemistry. Over Bi2Mo2O9 and Bi2MoO6, (E)-acrolein-3-d1:(Z)-acrolein-3-d1: acrolein-1-d1 was 1:1:1 consistent with a σ-allyl intermediate which rapidly converts between two equivalent forms (*CHDCHCH2 h CHDCH*CH2). With copper oxide, (E)-acrolein-3-d1: (Z)-acrolein-3-d1: acrolein-1-d1, was 1: 1: 1.6. This points to a discrimination isotope effect consistent with a σ-allyl intermediate without interconversion of equivalent forms. Over a Rh/α-Al2O3 catalyst, (E)-acrolein-3-d1: (Z)-acrolein-3-d1: acrolein-1-d1 was 1: 0.93: 0.89. This is consistent with an allyl intermediate along with a second minor nonallylic pathway which does not equilibrate the terminal carbon atoms. One or both of these processes occurred with some retention of the (E)-deuterium stereochemistry in the acrolein-3-d1. Over an unsupported Rh catalyst, (E)-acrolein-3-d1: (Z)-acrolein-3-d1: acrolein-1-d1 was 1: 0.68: 0.85. Only the allylic pathway is evident and the reaction process occurs with incomplete randomization (76 ± 10%) of the (E)-deuterium stereochemistry in the acrolein-3-d1.

Original languageEnglish (US)
Pages (from-to)355-364
Number of pages10
JournalJournal of Catalysis
Volume82
Issue number2
DOIs
StatePublished - Aug 1983
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Physical and Theoretical Chemistry

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