Issue 42, 2020

Palladium-catalysed methoxycarbonylation of ethene with bidentate diphosphine ligands: a density functional theory study

Abstract

Catalytic methoxycarbonylation of ethene with a bidentate tertiary phosphine (DTBPX) and palladium has been explored at the B3PW91-D3/PCM level of density functional theory. Three different pathways for formation of methyl propanoate (MePro) have been studied, namely carbomethoxy (A), ketene (B) and hydride-hydroxyalkylpalladium pathways (C), the latter of which is favoured because it has the lowest overall kinetic barrier. After intermolecular methanolysis, a hydroxyalkylpalladium complex has been characterised on pathway C, which eventually leads to the low overall barrier to produce MePro. The possibility of copolymerisation leading to oligo-/polymers has also been considered. With a computed selectivity of >99% towards the formation of MePro and a reasonably low overall kinetic barrier of 23.0 kcal mol−1, pathway C appears to be the most plausible one. Consistent with experimental data, the overall barrier increases to 30.1 kcal mol−1 for a less bulky bidentate phosphine.

Graphical abstract: Palladium-catalysed methoxycarbonylation of ethene with bidentate diphosphine ligands: a density functional theory study

Supplementary files

Article information

Article type
Paper
Submitted
22 Aug. 2020
Accepted
13 Okt. 2020
First published
13 Okt. 2020
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2020,22, 24330-24336

Palladium-catalysed methoxycarbonylation of ethene with bidentate diphosphine ligands: a density functional theory study

S. Ahmad, L. E. Crawford and M. Bühl, Phys. Chem. Chem. Phys., 2020, 22, 24330 DOI: 10.1039/D0CP04454G

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