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

Shahbaz Ahmad, Ashley Lockett, Timothy A Shuttleworth, Alexandra M Miles-Hobbs, Paul G Pringle, Michael Bühl

Research output: Contribution to journalArticle (Academic Journal)peer-review

4 Citations (Scopus)
42 Downloads (Pure)

Abstract

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 and η3-propen-1-oyl complexes that readily undergo methanolysis. With two hemilabile P,N-ligands and one or both of them protonated, the overall computed barrier is 16.8 kcal mol−1. 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-Me2N-Py)PPh2 and (6-Cl-Py)PPh2 ligands. 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
Volume21
Issue number16
Early online date26 Mar 2019
DOIs
Publication statusPublished - 17 Apr 2019

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