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Palladium–catalysed alkyne alkoxycarbonylation with P,N chelating ligands revisited: a density functional theory study

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Shahbaz Ahmad, Ashleigh Lockett, Timothy Shuttleworth, Alexandra Miles-Hobbs, Paul Pringle, Michael Buehl

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A revised in situ base mechanism of alkyne alkoxycarbonylation via a Pd catalyst with hemilabile P,N-ligands (PyPPh2, Py = 2-pyridyl) has been fully characterised at the B3PW91-D3/PCM level of density functional theory. Key intermediates on this route are acryloyl (η3-propen-1-oyl) complexes that readily undergo methanolysis. With two hemilabile P,N-ligands and one of them protonated, the overall computed barrier is 24.5 kcal mol-1, which decreases to 20.3 kcal mol-1 upon protonation of the second P,N-ligand. This new mechanism is consistent with all of the experimental data relating to substituent effects on relative reaction rates and branched/linear selectivities, including new results on the methoxycarbonylation of phenylacetylene using (4-NMe2Py)PPh2 and (6-Cl-Py)PPh2 ligand. This ligand is found to decrease catalytic activity over PyPPh2, thus invalidating a formerly characterised in situ base mechanism.


Original languageEnglish
Pages (from-to)8543-8552
Number of pages10
JournalPhysical Chemistry Chemical Physics
Issue number16
Early online date26 Mar 2019
Publication statusPublished - 28 Apr 2019

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