A cobalt hydride catalyst for the hydrogenation of CO2: Pathways for catalysis and deactivation

Matthew S. Jeletic, Monte L. Helm, Elliott B. Hulley, Michael T. Mock, Aaron M. Appel, John C. Linehan

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65 Citations (Scopus)

Abstract

The complex Co(dmpe)2H catalyzes the hydrogenation of CO2 at 1 atm and 21 °C with significant improvement in turnover frequency relative to previously reported second- and third-row transition-metal complexes. New studies are presented to elucidate the catalytic mechanism as well as pathways for catalyst deactivation. The catalytic rate was optimized through the choice of the base to match the pKa of the [Co(dmpe)2(H)2]+ intermediate. With a strong enough base, the catalytic rate has a zeroth-order dependence on the base concentration and the pressure of hydrogen and a first-order dependence on the pressure of CO2. However, for CO2:H2 ratios greater than 1, the catalytically inactive species [(μ-dmpe)(Co(dmpe)2)2]2+ and [Co(dmpe)2CO]+ were observed.

Original languageEnglish
Pages (from-to)3755-3762
Number of pages8
JournalACS Catalysis
Volume4
Issue number10
DOIs
Publication statusPublished - Oct 3 2014

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Keywords

  • CO
  • catalysis
  • cobalt
  • high-pressure NMR
  • hydrogenation

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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