Making a Splash in Homogeneous CO2 Hydrogenation

Elucidating the Impact of Solvent on Catalytic Mechanisms

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Molecular catalysts for hydrogenation of CO2 are widely studied as a means of chemical hydrogen storage. Catalysts are traditionally designed from the perspective of controlling the ligands bound to the metal. In recent years, studies have shown that the solvent can also play a key role in the mechanism of CO2 hydrogenation. A prominent example is the impact of the solvent on the thermodynamic hydride donor ability, or hydricity, of metal hydride complexes relative to the hydride acceptor ability of CO2. In some cases, simply changing from an organic solvent to water can reverse the direction of hydride transfer between a metal hydride and CO2. Additionally, the solvent can impact catalysis by converting CO2 into carbonate species, as well as activate intermediate products for hydrogenation to more reduced products. By understanding the substrate and product speciation, as well as the reactivity of the catalyst towards the substrate, the solvent can be used as a central design component for the rational development of new catalytic systems.

Original languageEnglish
JournalChemistry - A European Journal
DOIs
Publication statusAccepted/In press - Jan 1 2018

Fingerprint

Hydrides
Hydrogenation
Metals
Catalysts
Carbonates
Hydrogen storage
Substrates
Organic solvents
Catalysis
Ligands
Thermodynamics
Water

Keywords

  • Carbon dixode fixation
  • Homogeneous catalysis
  • Hydrides
  • Hydrogenation
  • Solvent effects

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Making a Splash in Homogeneous CO2 Hydrogenation: Elucidating the Impact of Solvent on Catalytic Mechanisms",
abstract = "Molecular catalysts for hydrogenation of CO2 are widely studied as a means of chemical hydrogen storage. Catalysts are traditionally designed from the perspective of controlling the ligands bound to the metal. In recent years, studies have shown that the solvent can also play a key role in the mechanism of CO2 hydrogenation. A prominent example is the impact of the solvent on the thermodynamic hydride donor ability, or hydricity, of metal hydride complexes relative to the hydride acceptor ability of CO2. In some cases, simply changing from an organic solvent to water can reverse the direction of hydride transfer between a metal hydride and CO2. Additionally, the solvent can impact catalysis by converting CO2 into carbonate species, as well as activate intermediate products for hydrogenation to more reduced products. By understanding the substrate and product speciation, as well as the reactivity of the catalyst towards the substrate, the solvent can be used as a central design component for the rational development of new catalytic systems.",
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AU - Linehan, John

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N2 - Molecular catalysts for hydrogenation of CO2 are widely studied as a means of chemical hydrogen storage. Catalysts are traditionally designed from the perspective of controlling the ligands bound to the metal. In recent years, studies have shown that the solvent can also play a key role in the mechanism of CO2 hydrogenation. A prominent example is the impact of the solvent on the thermodynamic hydride donor ability, or hydricity, of metal hydride complexes relative to the hydride acceptor ability of CO2. In some cases, simply changing from an organic solvent to water can reverse the direction of hydride transfer between a metal hydride and CO2. Additionally, the solvent can impact catalysis by converting CO2 into carbonate species, as well as activate intermediate products for hydrogenation to more reduced products. By understanding the substrate and product speciation, as well as the reactivity of the catalyst towards the substrate, the solvent can be used as a central design component for the rational development of new catalytic systems.

AB - Molecular catalysts for hydrogenation of CO2 are widely studied as a means of chemical hydrogen storage. Catalysts are traditionally designed from the perspective of controlling the ligands bound to the metal. In recent years, studies have shown that the solvent can also play a key role in the mechanism of CO2 hydrogenation. A prominent example is the impact of the solvent on the thermodynamic hydride donor ability, or hydricity, of metal hydride complexes relative to the hydride acceptor ability of CO2. In some cases, simply changing from an organic solvent to water can reverse the direction of hydride transfer between a metal hydride and CO2. Additionally, the solvent can impact catalysis by converting CO2 into carbonate species, as well as activate intermediate products for hydrogenation to more reduced products. By understanding the substrate and product speciation, as well as the reactivity of the catalyst towards the substrate, the solvent can be used as a central design component for the rational development of new catalytic systems.

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