Changing the Mechanism for CO2 Hydrogenation Using Solvent-Dependent Thermodynamics

Samantha A. Burgess, Aaron Appel, John Linehan, Eric Wiedner

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17 Citations (Scopus)

Abstract

A critical scientific challenge for utilization of CO2 is the development of catalyst systems that function in water and use inexpensive and environmentally friendly reagents. We have used thermodynamic insights to predict and demonstrate that the HCoI(dmpe)2 catalyst system, previously described for use in organic solvents, can hydrogenate CO2 to formate in water with bicarbonate as the only added reagent. Replacing tetrahydrofuran as the solvent with water changes the mechanism for catalysis by altering the thermodynamics for hydride transfer to CO2 from a key dihydride intermediate. The need for a strong organic base was eliminated by performing catalysis in water owing to the change in mechanism. These studies demonstrate that the solvent plays a pivotal role in determining the reaction thermodynamics and thereby catalytic mechanism and activity.

Original languageEnglish
Pages (from-to)15002-15005
Number of pages4
JournalAngewandte Chemie - International Edition
Volume56
Issue number47
DOIs
Publication statusPublished - Nov 20 2017

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Keywords

  • carbon dioxide fixation
  • homogeneous catalysis
  • hydricity
  • hydrogenation
  • solvent effects

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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