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https://hdl.handle.net/2440/47619
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Type: | Journal article |
Title: | Regioselective control of the nickel-mediated coupling of acetylene and carbon dioxide - A DFT study |
Author: | Graham, D. Bruce, M. Metha, G. Bowie, J. Buntine, M. |
Citation: | Journal of Organometallic Chemistry, 2008; 693(16):2703-2710 |
Publisher: | Elsevier Science Sa |
Issue Date: | 2008 |
ISSN: | 0022-328X 1872-8561 |
Statement of Responsibility: | David C. Graham, Michael I. Bruce, Gregory F. Metha, John H. Bowie and Mark A. Buntine |
Abstract: | 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). |
Description: | Copyright © 2008 Elsevier B.V. All rights reserved. |
DOI: | 10.1016/j.jorganchem.2008.05.015 |
Description (link): | http://www.elsevier.com/wps/find/journaldescription.cws_home/504090/description#description |
Published version: | http://dx.doi.org/10.1016/j.jorganchem.2008.05.015 |
Appears in Collections: | Aurora harvest Chemistry publications Environment Institute publications |
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