Regioselective control of the nickel-mediated coupling of acetylene and carbon dioxide - A DFT study
The nickel-mediated coupling of asymmetric alkynes with carbon dioxide is known to be highly regioselective with respect to the formation of nickelacycle intermediates and α,β-unsaturated carboxylic acid products. Using density functional theory (DFT), we have investigated the effect that parameters...
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| Format: | Journal Article |
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Elsevier
2008
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| Online Access: | http://hdl.handle.net/20.500.11937/15784 |
| _version_ | 1848748987477131264 |
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| author | Graham, D. Bruce, M. Bowie, J. Buntine, Mark |
| author_facet | Graham, D. Bruce, M. Bowie, J. Buntine, Mark |
| author_sort | Graham, D. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | The nickel-mediated coupling of asymmetric alkynes with carbon dioxide is known to be highly regioselective with respect to the formation of nickelacycle intermediates and α,β-unsaturated carboxylic acid products. Using density functional theory (DFT), we have investigated the effect that parameters such as acetylene-substituent, ancillary ligand and solvent have on the potential energy surface of the nickelacycle coupling reaction. 3-R-substituted nickelacycles are the thermodynamically preferred product in all cases surveyed, however, the transition structure characterised by the attack of CO2 on the alkyne carbon distal from the R-group is generally lower in energy, making the 2-R-substituted nickelacycle the kinetically favoured product. Ligating the zerovalent nickel species with the diazabicyclo[5.4.0]undec-7-ene (DBU) ancillary ligand in preference to 2,2′-bipyridine (BIPY) leads to lower activation energies for the coupling reaction and products that are less susceptible to steric bulk in the 2-position of the nickelacycle. Solvation with dimethylformamide (DMF) has the advantage of lowering the activation barrier for the coupling reaction when compared to tetrahydrofuran (THF). |
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| format | Journal Article |
| id | curtin-20.500.11937-15784 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T07:13:46Z |
| publishDate | 2008 |
| publisher | Elsevier |
| recordtype | eprints |
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| spelling | curtin-20.500.11937-157842017-09-13T16:09:33Z Regioselective control of the nickel-mediated coupling of acetylene and carbon dioxide - A DFT study Graham, D. Bruce, M. Bowie, J. Buntine, Mark Augmented basis-sets Electrochemical carboxylation Terminal alkynes Oxanickelacyclopentene complex Alkenes Homogeneous hydrogenation CO2 Ab-initio Polarizable continuum model Anion calculations The nickel-mediated coupling of asymmetric alkynes with carbon dioxide is known to be highly regioselective with respect to the formation of nickelacycle intermediates and α,β-unsaturated carboxylic acid products. Using density functional theory (DFT), we have investigated the effect that parameters such as acetylene-substituent, ancillary ligand and solvent have on the potential energy surface of the nickelacycle coupling reaction. 3-R-substituted nickelacycles are the thermodynamically preferred product in all cases surveyed, however, the transition structure characterised by the attack of CO2 on the alkyne carbon distal from the R-group is generally lower in energy, making the 2-R-substituted nickelacycle the kinetically favoured product. Ligating the zerovalent nickel species with the diazabicyclo[5.4.0]undec-7-ene (DBU) ancillary ligand in preference to 2,2′-bipyridine (BIPY) leads to lower activation energies for the coupling reaction and products that are less susceptible to steric bulk in the 2-position of the nickelacycle. Solvation with dimethylformamide (DMF) has the advantage of lowering the activation barrier for the coupling reaction when compared to tetrahydrofuran (THF). 2008 Journal Article http://hdl.handle.net/20.500.11937/15784 10.1016/j.jorganchem.2008.05.015 Elsevier restricted |
| spellingShingle | Augmented basis-sets Electrochemical carboxylation Terminal alkynes Oxanickelacyclopentene complex Alkenes Homogeneous hydrogenation CO2 Ab-initio Polarizable continuum model Anion calculations Graham, D. Bruce, M. Bowie, J. Buntine, Mark Regioselective control of the nickel-mediated coupling of acetylene and carbon dioxide - A DFT study |
| title | Regioselective control of the nickel-mediated coupling of acetylene and carbon dioxide - A DFT study |
| title_full | Regioselective control of the nickel-mediated coupling of acetylene and carbon dioxide - A DFT study |
| title_fullStr | Regioselective control of the nickel-mediated coupling of acetylene and carbon dioxide - A DFT study |
| title_full_unstemmed | Regioselective control of the nickel-mediated coupling of acetylene and carbon dioxide - A DFT study |
| title_short | Regioselective control of the nickel-mediated coupling of acetylene and carbon dioxide - A DFT study |
| title_sort | regioselective control of the nickel-mediated coupling of acetylene and carbon dioxide - a dft study |
| topic | Augmented basis-sets Electrochemical carboxylation Terminal alkynes Oxanickelacyclopentene complex Alkenes Homogeneous hydrogenation CO2 Ab-initio Polarizable continuum model Anion calculations |
| url | http://hdl.handle.net/20.500.11937/15784 |