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Title: Catalytic hydrogenation of carbon monoxide

Abstract

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 intermediatesmore » 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.« less

Authors:
Publication Date:
Research Org.:
Pennsylvania Univ., Philadelphia, PA (United States). Dept. of Chemistry
Sponsoring Org.:
USDOE; USDOE, Washington, DC (United States)
OSTI Identifier:
5260923
Report Number(s):
DOE/ER/13615-6
ON: DE92014729
DOE Contract Number:
FG02-86ER13615
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
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; 400201* - Chemical & Physicochemical Properties

Citation Formats

Wayland, B.B. Catalytic hydrogenation of carbon monoxide. United States: N. p., 1992. Web. doi:10.2172/5260923.
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Wayland, B.B. Catalytic hydrogenation of carbon monoxide. United States. doi:10.2172/5260923.
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Wayland, B.B. Tue . "Catalytic hydrogenation of carbon monoxide". United States. doi:10.2172/5260923. https://www.osti.gov/servlets/purl/5260923.
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@article{osti_5260923,
title = {Catalytic hydrogenation of carbon monoxide},
author = {Wayland, B.B.},
abstractNote = {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.},
doi = {10.2172/5260923},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Tue Dec 01 00:00:00 EST 1992},
month = {Tue Dec 01 00:00:00 EST 1992}
}
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Technical Report:
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DOI:  10.2172/5260923
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  • Objective is to learn how to utilize the unique properties of rhodium porphyrins in achieving catalytic hydrogenation of carbon monoxide at mild conditions. Rhodium porphyrins react with H/sub 2/ and CO at pressures less than one atmosphere to produce the first intermediate in the hydrogenation of CO and provide a realistic opportunity to participate in the catalytic hydrogenation of CO at low gas pressures. Several catalytic schemes are proposed which take advantage of the unique reactivity of rhodium porphyrins coupled with the aldehyde-like character of the metallo formyl intermediate. Multifunctional catalysts that utilize rhodium porphyrins and a second catalyst knownmore » to promote the hydrogenation of aldehydes are particularly promising candidates for achieving low pressure hydrogenation of CO. Solvent effects will be explored as one means for tuning the thermodynamic and kinetic parameters for optimum catalytic behavior. Comparative studies utilizing variation of the macrocycle and central metal (Co,Rh,Ir) are being used in identifying the essential features required to obtain a catalyst system based on metallo macrocycles.« less

  • Title: Catalytic Hydrogenation of Carbon Monoxide and Olefin Oxidation Grant No. DE-FG02-86ER13615 PI: Wayland, B. B. (wayland@sas.upenn.edu) Abstract Development of new mechanistic strategies and catalyst materials for activation of CO, H2, CH4, C2H4, O2, and related substrates relevant to the conversion of carbon monoxide, alkanes, and alkenes to organic oxygenates are central objectives encompassed by this program. Design and synthesis of metal complexes that manifest reactivity patterns associated with potential pathways for the hydrogenation of carbon monoxide through metallo-formyl (M-CHO), dimetal ketone (M-C(O)-M), and dimetal dionyl (M-C(O)-C(O)-M) species is one major focus. Hydrocarbon oxidation using molecular oxygen is a centralmore » goal for methane activation and functionalization as well as regioselective oxidation of olefins. Discovery of new reactivity patterns and control of selectivity are pursued through designing new metal complexes and adjusting reaction conditions. Variation of reaction media promotes distinct reaction pathways that control both reaction rates and selectivities. Dimetalloradical diporphyrin complexes preorganize transition states for substrate reactions that involve two metal centers and manifest large rate increases over mono-metalloradical reactions of hydrogen, methane, and other small molecule substrates. Another broad goal and recurring theme of this program is to contribute to the thermodynamic database for a wide scope of organo-metal transformations in a range of reaction media. One of the most complete descriptions of equilibrium thermodynamics for organometallic reactions in water and methanol is emerging from the study of rhodium porphyrin substrate reactions in aqueous and alcoholic media. Water soluble group nine metalloporphyrins manifest remarkably versatile substrate reactivity in aqueous and alcoholic media which includes producing rhodium formyl (Rh-CHO) and hydroxy methyl (Rh-CH2OH) species. Exploratory directions for this program include expending new strategies for anti-Markovnikov addition of water, alcohols, and amines with olefins, developing catalytic reactions of CO to give formamides and formic esters, and evaluating the potential for coupling reactions of CO to produce organic building blocks.« less

  • The principal objective of this program is to learn how to utilize the unique porperties of Rhodium porphyrins in achieving catalytic hydrogenation of carbon monoxide at mild conditions. Rhodium porphyrins react with H/sub 2/ and CO at pressures less than one atmosphere to produce the first intermediate in the hydrogenation of CO and provide a realistic opportunity to participate in the catalytic hydrogenation of CO at low gas pressures. Several catalytic schemes are porposed which take advantage of the unique reactivity of Rhodium porphyrins coupled with the aldehyde-like character of the metallo formyl intermediate. Multifunctional catalysts that utilize Rhodium porphyrinsmore » and a second catalyst known to promote the hydrogenation of aldehydes are particularly promising candidates for achieving low pressure hydrogenation of CO. Solvent effects will be explored as one means for tuning the thermodynamic and kinetic parameters for optimum catalytic behavior. Comparative studies used in identifying the essential features required to obtain a catalyst system based on metallo macrocycles.« less

  • The effect of additives on catalysts for the hydrogenation of carbon monoxide and the cyclotromerization of acetylene has been investigated using both low pressure surface science techniques and high pressure reaction studies. Additives were found to have relatively complicated catalytic behavior, which could be explained with the aid of surface analytical tools such as AES, XPS, TPD, and LEED. Potassium was found to have the greatest effect on both the hydrogenation of CO and the cyclotrimerization of acetylene over all metal catalysts. For CO hydrogenation over Rh, a large equilibrium deuterium isotope effect was observed.

  • The primary focus of this project is on developing new approaches for the hydrogenation of carbon monoxide at mild conditions. Our strategies are based on the favorable thermodynamics of rhodium macrocycles implicated in the catalytic hydrogenation of CO. Metalloformyl complexes and CO reductive coupling provide alternate routes to organic oxygenates that utilize these species as intermediates. Thermodynamic and kinetic-mechanistic studies are used in guiding the design of new metallospecies to improve the thermodynamic and kinetic factors for individual steps in the overall process. Electronic and steric effects associated with the ligand arrays along with the influences of the reaction mediummore » provide the chemical tools for tuning these factors. Non-macrocyclic ligand complexes that emulate rhodium macrocycles, but with improved reaction kinetics are promising materials for future development. 6 refs.« less