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    Regioselective control of the nickel-mediated coupling of acetylene and carbon dioxide - A DFT study

    Access Status
    Fulltext not available
    Authors
    Graham, D.
    Bruce, M.
    Bowie, J.
    Buntine, Mark
    Date
    2008
    Type
    Journal Article
    
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    Citation
    Graham, David C. and Bruce, Michael I. and Metha, Gregory F. and Bowie, John H. and Buntine, Mark A. 2008. Regioselective control of the nickel-mediated coupling of acetylene and carbon dioxide - A DFT study. Journal of Organometallic Chemistry 693 (16): pp. 2703-2710.
    Source Title
    Journal of Organometallic Chemistry
    DOI
    10.1016/j.jorganchem.2008.05.015
    ISSN
    0022328X
    URI
    http://hdl.handle.net/20.500.11937/15784
    Collection
    • Curtin Research Publications
    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).

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