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Competing reaction mechanisms for the carbonylation of neutral palladium(II) complexes containing bidentate ligands: a theoretical study
Citation
Frankcombe, KE and Cavell, KJ and Yates, BF and Knott, RB, Competing reaction mechanisms for the carbonylation of neutral palladium(II) complexes containing bidentate ligands: a theoretical study, Organometallics, 16, (14) pp. 3199-3206. ISSN 0276-7333 (1997) [Refereed Article]
Abstract
The complete carbonylation mechanism for the model palladium(II) system, Pd(PH3)(CH3)-(N-O) + CO → Pd(PH3)(COCH3)(N-O) (N-O = NHCHCOO-), has been investigated employing nonlocal density functional theory (DFT) and second-order Mø11er-Plesset perturbation theory (MP2). Four possible mechanisms were identified, all involving the initial displacement of the phosphine ligand by carbon monoxide via a trigonal bipyramidal transition structure. Of these four mechanisms, the rate-determining methyl migration step was found to be lowest in energy when proceeding from a novel five-coordinate intermediate in which the palladium-nitrogen bond is weakened (2.385 Å at the MP2 level of theory). This mechanism is consistent with the available experimental data. MP2 calculations using large basis sets predicted an overall exothermicity of -59.7 kJ/mol and a negligible activation energy of +6.0 kJ/mol with respect to the separated reactants. In addition, a novel transition structure that accounts for the isomerization of square-pyramidal d8 complexes is presented.
Item Details
Item Type: | Refereed Article |
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Research Division: | Chemical Sciences |
Research Group: | Theoretical and computational chemistry |
Research Field: | Theoretical and computational chemistry not elsewhere classified |
Objective Division: | Expanding Knowledge |
Objective Group: | Expanding knowledge |
Objective Field: | Expanding knowledge in the chemical sciences |
UTAS Author: | Frankcombe, KE (Ms Katrina Ellen Frankcombe) |
UTAS Author: | Cavell, KJ (Professor Kingsley Cavell) |
UTAS Author: | Yates, BF (Professor Brian Yates) |
ID Code: | 11939 |
Year Published: | 1997 |
Web of Science® Times Cited: | 26 |
Deposited By: | Chemistry |
Deposited On: | 1997-08-01 |
Last Modified: | 2011-08-15 |
Downloads: | 0 |
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