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 avq 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

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements