Catalytic hydrogenation of carbon monoxide
This project is focused on developing strategies to accomplish the reduction and hydrogenation of carbon monoxide to produce organic oxygenates at mild conditions. Our approaches to this issue are based on the recognition that rhodium macrocycles have unusually favorable thermodynamic values for pro...
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ftosti:oai:osti.gov:5260923 2023-07-30T04:02:56+02:00 Catalytic hydrogenation of carbon monoxide Wayland, B.B. 2008-06-30 application/pdf http://www.osti.gov/servlets/purl/5260923 https://www.osti.gov/biblio/5260923 https://doi.org/10.2172/5260923 unknown http://www.osti.gov/servlets/purl/5260923 https://www.osti.gov/biblio/5260923 https://doi.org/10.2172/5260923 doi:10.2172/5260923 37 INORGANIC ORGANIC PHYSICAL AND ANALYTICAL CHEMISTRY ALKENES CHEMICAL ACTIVATION CARBON MONOXIDE HYDROGENATION CATALYTIC EFFECTS DISSOCIATION HEAT ISONITRILES ORGANOMETALLIC COMPOUNDS PORPHYRINS PROGRESS REPORT RADICALS RHODIUM COMPLEXES THERMODYNAMICS CARBON COMPOUNDS CARBON OXIDES CARBONIC ACID DERIVATIVES CARBOXYLIC ACIDS CHALCOGENIDES CHEMICAL REACTIONS COMPLEXES DOCUMENT TYPES ENTHALPY HETEROCYCLIC ACIDS HETEROCYCLIC COMPOUNDS HYDROCARBONS ORGANIC ACIDS ORGANIC COMPOUNDS ORGANIC NITROGEN COMPOUNDS OXIDES OXYGEN COMPOUNDS PHYSICAL PROPERTIES REACTION HEAT THERMODYNAMIC PROPERTIES TRANSITION ELEMENT COMPLEXES 2008 ftosti https://doi.org/10.2172/5260923 2023-07-11T10:38:09Z This project is focused on developing strategies to accomplish the reduction and hydrogenation of carbon monoxide to produce organic oxygenates at mild conditions. Our approaches to this issue are based on the recognition that rhodium macrocycles have unusually favorable thermodynamic values for producing a series of intermediate implicated in the catalytic hydrogenation of CO. Observations of metalloformyl complexes produced by reactions of H{sub 2} and CO, and reductive coupling of CO to form metallo {alpha}-diketone species have suggested a multiplicity of routes to organic oxygenates that utilize these species as intermediates. Thermodynamic and kinetic-mechanistic studies are used in constructing energy profiles for a variety of potential pathways, and these schemes are used in guiding the design of new metallospecies to improve the thermodynamic and kinetic factors for individual steps in the overall process. Variation of the electronic and steric effects associated with the ligand arrays along with the influences of the reaction medium provide the chemical tools for tuning these factors. Emerging knowledge of the factors that contribute to M-H, M-C and M-O bond enthalpies is directing the search for ligand arrays that will expand the range of metal species that have favorable thermodynamic parameters to produce the primary intermediates for CO hydrogenation. Studies of rhodium complexes are being extended to non-macrocyclic ligand complexes that emulate the favorable thermodynamic features associated with rhodium macrocycles, but that also manifest improved reaction kinetics. Multifunctional catalyst systems designed to couple the ability of rhodium complexes to produce formyl and diketone intermediates with a second catalyst that hydrogenates these imtermediates are promising approaches to accomplish CO hydrogenation at mild conditions. Other/Unknown Material Carbonic acid SciTec Connect (Office of Scientific and Technical Information - OSTI, U.S. Department of Energy) |
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SciTec Connect (Office of Scientific and Technical Information - OSTI, U.S. Department of Energy) |
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37 INORGANIC ORGANIC PHYSICAL AND ANALYTICAL CHEMISTRY ALKENES CHEMICAL ACTIVATION CARBON MONOXIDE HYDROGENATION CATALYTIC EFFECTS DISSOCIATION HEAT ISONITRILES ORGANOMETALLIC COMPOUNDS PORPHYRINS PROGRESS REPORT RADICALS RHODIUM COMPLEXES THERMODYNAMICS CARBON COMPOUNDS CARBON OXIDES CARBONIC ACID DERIVATIVES CARBOXYLIC ACIDS CHALCOGENIDES CHEMICAL REACTIONS COMPLEXES DOCUMENT TYPES ENTHALPY HETEROCYCLIC ACIDS HETEROCYCLIC COMPOUNDS HYDROCARBONS ORGANIC ACIDS ORGANIC COMPOUNDS ORGANIC NITROGEN COMPOUNDS OXIDES OXYGEN COMPOUNDS PHYSICAL PROPERTIES REACTION HEAT THERMODYNAMIC PROPERTIES TRANSITION ELEMENT COMPLEXES |
spellingShingle |
37 INORGANIC ORGANIC PHYSICAL AND ANALYTICAL CHEMISTRY ALKENES CHEMICAL ACTIVATION CARBON MONOXIDE HYDROGENATION CATALYTIC EFFECTS DISSOCIATION HEAT ISONITRILES ORGANOMETALLIC COMPOUNDS PORPHYRINS PROGRESS REPORT RADICALS RHODIUM COMPLEXES THERMODYNAMICS CARBON COMPOUNDS CARBON OXIDES CARBONIC ACID DERIVATIVES CARBOXYLIC ACIDS CHALCOGENIDES CHEMICAL REACTIONS COMPLEXES DOCUMENT TYPES ENTHALPY HETEROCYCLIC ACIDS HETEROCYCLIC COMPOUNDS HYDROCARBONS ORGANIC ACIDS ORGANIC COMPOUNDS ORGANIC NITROGEN COMPOUNDS OXIDES OXYGEN COMPOUNDS PHYSICAL PROPERTIES REACTION HEAT THERMODYNAMIC PROPERTIES TRANSITION ELEMENT COMPLEXES Wayland, B.B. Catalytic hydrogenation of carbon monoxide |
topic_facet |
37 INORGANIC ORGANIC PHYSICAL AND ANALYTICAL CHEMISTRY ALKENES CHEMICAL ACTIVATION CARBON MONOXIDE HYDROGENATION CATALYTIC EFFECTS DISSOCIATION HEAT ISONITRILES ORGANOMETALLIC COMPOUNDS PORPHYRINS PROGRESS REPORT RADICALS RHODIUM COMPLEXES THERMODYNAMICS CARBON COMPOUNDS CARBON OXIDES CARBONIC ACID DERIVATIVES CARBOXYLIC ACIDS CHALCOGENIDES CHEMICAL REACTIONS COMPLEXES DOCUMENT TYPES ENTHALPY HETEROCYCLIC ACIDS HETEROCYCLIC COMPOUNDS HYDROCARBONS ORGANIC ACIDS ORGANIC COMPOUNDS ORGANIC NITROGEN COMPOUNDS OXIDES OXYGEN COMPOUNDS PHYSICAL PROPERTIES REACTION HEAT THERMODYNAMIC PROPERTIES TRANSITION ELEMENT COMPLEXES |
description |
This project is focused on developing strategies to accomplish the reduction and hydrogenation of carbon monoxide to produce organic oxygenates at mild conditions. Our approaches to this issue are based on the recognition that rhodium macrocycles have unusually favorable thermodynamic values for producing a series of intermediate implicated in the catalytic hydrogenation of CO. Observations of metalloformyl complexes produced by reactions of H{sub 2} and CO, and reductive coupling of CO to form metallo {alpha}-diketone species have suggested a multiplicity of routes to organic oxygenates that utilize these species as intermediates. Thermodynamic and kinetic-mechanistic studies are used in constructing energy profiles for a variety of potential pathways, and these schemes are used in guiding the design of new metallospecies to improve the thermodynamic and kinetic factors for individual steps in the overall process. Variation of the electronic and steric effects associated with the ligand arrays along with the influences of the reaction medium provide the chemical tools for tuning these factors. Emerging knowledge of the factors that contribute to M-H, M-C and M-O bond enthalpies is directing the search for ligand arrays that will expand the range of metal species that have favorable thermodynamic parameters to produce the primary intermediates for CO hydrogenation. Studies of rhodium complexes are being extended to non-macrocyclic ligand complexes that emulate the favorable thermodynamic features associated with rhodium macrocycles, but that also manifest improved reaction kinetics. Multifunctional catalyst systems designed to couple the ability of rhodium complexes to produce formyl and diketone intermediates with a second catalyst that hydrogenates these imtermediates are promising approaches to accomplish CO hydrogenation at mild conditions. |
author |
Wayland, B.B. |
author_facet |
Wayland, B.B. |
author_sort |
Wayland, B.B. |
title |
Catalytic hydrogenation of carbon monoxide |
title_short |
Catalytic hydrogenation of carbon monoxide |
title_full |
Catalytic hydrogenation of carbon monoxide |
title_fullStr |
Catalytic hydrogenation of carbon monoxide |
title_full_unstemmed |
Catalytic hydrogenation of carbon monoxide |
title_sort |
catalytic hydrogenation of carbon monoxide |
publishDate |
2008 |
url |
http://www.osti.gov/servlets/purl/5260923 https://www.osti.gov/biblio/5260923 https://doi.org/10.2172/5260923 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_relation |
http://www.osti.gov/servlets/purl/5260923 https://www.osti.gov/biblio/5260923 https://doi.org/10.2172/5260923 doi:10.2172/5260923 |
op_doi |
https://doi.org/10.2172/5260923 |
_version_ |
1772813842174181376 |