Transition metal activation and functionalization of carbon-hydrogen bonds
We are investigating the fundamental thermodynamic and kinetic factors that influence carbon-hydrogen bond activation at homogeneous transition metal centers and the conversion of hydrocarbons into functionalized products of potential use to the chemical industry. Advances have been made in both und...
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ftosti:oai:osti.gov:5157271 2023-07-30T04:02:56+02:00 Transition metal activation and functionalization of carbon-hydrogen bonds Jones, W.D. 2008-06-30 application/pdf http://www.osti.gov/servlets/purl/5157271 https://www.osti.gov/biblio/5157271 https://doi.org/10.2172/5157271 unknown http://www.osti.gov/servlets/purl/5157271 https://www.osti.gov/biblio/5157271 https://doi.org/10.2172/5157271 doi:10.2172/5157271 37 INORGANIC ORGANIC PHYSICAL AND ANALYTICAL CHEMISTRY AROMATICS PHOTOCHEMICAL REACTIONS HETEROCYCLIC COMPOUNDS ISONITRILES RHODIUM COMPLEXES CATALYTIC EFFECTS BORATES CHEMICAL ACTIVATION FURANS ORGANOMETALLIC COMPOUNDS PROGRESS REPORT PYRAZOLES PYRROLES THIOPHENE AZOLES BORON COMPOUNDS CARBONIC ACID DERIVATIVES CHEMICAL REACTIONS COMPLEXES DOCUMENT TYPES ORGANIC COMPOUNDS ORGANIC NITROGEN COMPOUNDS ORGANIC OXYGEN COMPOUNDS ORGANIC SULFUR COMPOUNDS OXYGEN COMPOUNDS TRANSITION ELEMENT COMPLEXES 2008 ftosti https://doi.org/10.2172/5157271 2023-07-11T10:37:05Z We are investigating the fundamental thermodynamic and kinetic factors that influence carbon-hydrogen bond activation at homogeneous transition metal centers and the conversion of hydrocarbons into functionalized products of potential use to the chemical industry. Advances have been made in both understanding the interactions of hydrocarbons with metals and in the functionalization of hydrocarbons. We have found that RhCl(PR{sub 3}){sub 2}(CNR) complexes can catalyze the insertion of isonitriles into the C-H bonds or arenes upon photolysis. The mechanism of these reactions was found to proceed by way of initial phosphine dissociation, followed by C-H activation and isonitrile insertion. We have also examined reactions of a series of arenes with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and begun to map out the kinetic and thermodynamic preferences for arene coordination. The effects of resonance, specifically the differences in the Hueckel energies of the bound vs free ligand, are now believed to fully control the C-H activation/{eta}{sup 2}-coordination equilibria. We have begun to examine the reactions of rhodium isonitrile pyrazolylborates for alkane and arene C-H bond activation. A new, labile, carbodiimide precursor has been developed for these studies. We have completed studies of the reactions of (C{sub 5}Me{sub 5})Rh(PMe{sub 3})H{sub 2} with D{sub 2} and PMe{sub 3} that indicate that both {eta}{sup 5} {yields} {eta}{sup 3} ring slippage and metal to ring hydride migration occur more facilely than thermal reductive elimination of H{sub 2}. We have examined the reactions of heterocycles with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and found that pyrrole and furan undergo C-H or N-H activation. Thiophene, however, undergoes C-S bond oxidative addition, and the mechanism of activation has been shown to proceed through sulfur coordination prior to C-S insertion. Other/Unknown Material Carbonic acid SciTec Connect (Office of Scientific and Technical Information - OSTI, U.S. Department of Energy) Eta ENVELOPE(-62.917,-62.917,-64.300,-64.300) |
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SciTec Connect (Office of Scientific and Technical Information - OSTI, U.S. Department of Energy) |
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ftosti |
language |
unknown |
topic |
37 INORGANIC ORGANIC PHYSICAL AND ANALYTICAL CHEMISTRY AROMATICS PHOTOCHEMICAL REACTIONS HETEROCYCLIC COMPOUNDS ISONITRILES RHODIUM COMPLEXES CATALYTIC EFFECTS BORATES CHEMICAL ACTIVATION FURANS ORGANOMETALLIC COMPOUNDS PROGRESS REPORT PYRAZOLES PYRROLES THIOPHENE AZOLES BORON COMPOUNDS CARBONIC ACID DERIVATIVES CHEMICAL REACTIONS COMPLEXES DOCUMENT TYPES ORGANIC COMPOUNDS ORGANIC NITROGEN COMPOUNDS ORGANIC OXYGEN COMPOUNDS ORGANIC SULFUR COMPOUNDS OXYGEN COMPOUNDS TRANSITION ELEMENT COMPLEXES |
spellingShingle |
37 INORGANIC ORGANIC PHYSICAL AND ANALYTICAL CHEMISTRY AROMATICS PHOTOCHEMICAL REACTIONS HETEROCYCLIC COMPOUNDS ISONITRILES RHODIUM COMPLEXES CATALYTIC EFFECTS BORATES CHEMICAL ACTIVATION FURANS ORGANOMETALLIC COMPOUNDS PROGRESS REPORT PYRAZOLES PYRROLES THIOPHENE AZOLES BORON COMPOUNDS CARBONIC ACID DERIVATIVES CHEMICAL REACTIONS COMPLEXES DOCUMENT TYPES ORGANIC COMPOUNDS ORGANIC NITROGEN COMPOUNDS ORGANIC OXYGEN COMPOUNDS ORGANIC SULFUR COMPOUNDS OXYGEN COMPOUNDS TRANSITION ELEMENT COMPLEXES Jones, W.D. Transition metal activation and functionalization of carbon-hydrogen bonds |
topic_facet |
37 INORGANIC ORGANIC PHYSICAL AND ANALYTICAL CHEMISTRY AROMATICS PHOTOCHEMICAL REACTIONS HETEROCYCLIC COMPOUNDS ISONITRILES RHODIUM COMPLEXES CATALYTIC EFFECTS BORATES CHEMICAL ACTIVATION FURANS ORGANOMETALLIC COMPOUNDS PROGRESS REPORT PYRAZOLES PYRROLES THIOPHENE AZOLES BORON COMPOUNDS CARBONIC ACID DERIVATIVES CHEMICAL REACTIONS COMPLEXES DOCUMENT TYPES ORGANIC COMPOUNDS ORGANIC NITROGEN COMPOUNDS ORGANIC OXYGEN COMPOUNDS ORGANIC SULFUR COMPOUNDS OXYGEN COMPOUNDS TRANSITION ELEMENT COMPLEXES |
description |
We are investigating the fundamental thermodynamic and kinetic factors that influence carbon-hydrogen bond activation at homogeneous transition metal centers and the conversion of hydrocarbons into functionalized products of potential use to the chemical industry. Advances have been made in both understanding the interactions of hydrocarbons with metals and in the functionalization of hydrocarbons. We have found that RhCl(PR{sub 3}){sub 2}(CNR) complexes can catalyze the insertion of isonitriles into the C-H bonds or arenes upon photolysis. The mechanism of these reactions was found to proceed by way of initial phosphine dissociation, followed by C-H activation and isonitrile insertion. We have also examined reactions of a series of arenes with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and begun to map out the kinetic and thermodynamic preferences for arene coordination. The effects of resonance, specifically the differences in the Hueckel energies of the bound vs free ligand, are now believed to fully control the C-H activation/{eta}{sup 2}-coordination equilibria. We have begun to examine the reactions of rhodium isonitrile pyrazolylborates for alkane and arene C-H bond activation. A new, labile, carbodiimide precursor has been developed for these studies. We have completed studies of the reactions of (C{sub 5}Me{sub 5})Rh(PMe{sub 3})H{sub 2} with D{sub 2} and PMe{sub 3} that indicate that both {eta}{sup 5} {yields} {eta}{sup 3} ring slippage and metal to ring hydride migration occur more facilely than thermal reductive elimination of H{sub 2}. We have examined the reactions of heterocycles with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and found that pyrrole and furan undergo C-H or N-H activation. Thiophene, however, undergoes C-S bond oxidative addition, and the mechanism of activation has been shown to proceed through sulfur coordination prior to C-S insertion. |
author |
Jones, W.D. |
author_facet |
Jones, W.D. |
author_sort |
Jones, W.D. |
title |
Transition metal activation and functionalization of carbon-hydrogen bonds |
title_short |
Transition metal activation and functionalization of carbon-hydrogen bonds |
title_full |
Transition metal activation and functionalization of carbon-hydrogen bonds |
title_fullStr |
Transition metal activation and functionalization of carbon-hydrogen bonds |
title_full_unstemmed |
Transition metal activation and functionalization of carbon-hydrogen bonds |
title_sort |
transition metal activation and functionalization of carbon-hydrogen bonds |
publishDate |
2008 |
url |
http://www.osti.gov/servlets/purl/5157271 https://www.osti.gov/biblio/5157271 https://doi.org/10.2172/5157271 |
long_lat |
ENVELOPE(-62.917,-62.917,-64.300,-64.300) |
geographic |
Eta |
geographic_facet |
Eta |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_relation |
http://www.osti.gov/servlets/purl/5157271 https://www.osti.gov/biblio/5157271 https://doi.org/10.2172/5157271 doi:10.2172/5157271 |
op_doi |
https://doi.org/10.2172/5157271 |
_version_ |
1772813848147918848 |