The University of Southampton
University of Southampton Institutional Repository

Ferrocenylmethylphosphanes and the alpha process for Methoxycarbonylation: The Original Story

Ferrocenylmethylphosphanes and the alpha process for Methoxycarbonylation: The Original Story
Ferrocenylmethylphosphanes and the alpha process for Methoxycarbonylation: The Original Story
The Lucite Alpha process is the predominant technology for the preparation of acrylics. This two-stage process involves the palladium-catalysed formation of methyl propanoate from ethene, CO, and methanol, followed by the oxidative formylation of methyl propanoate into methyl methacrylate. A range of bis-1,2-disubstituted aminomethylferrocenes has been prepared and characterised. These complexes serve as precursors to a variety of bulky ferrocenylmethyldiphosphanes that, in turn, function as ligands in the palladium-catalysed process. We describe the crystal structures of five ligand precursors and provide a rationale for their design. In situ catalyst testing on palladium complexes derived from ferrocenylphosphanes demonstrates that these are highly selective (>99.5%) catalysts for the formation of methyl propanoate from ethene, CO, and methanol and have turnover numbers exceeding 50,000. This article credits those researchers who worked on this project in the early days, who received little or no credit for their achievements and endeavours.
Catalysis, Ferrocene, Ligand, Methoxycarbonylation, Palladium, Phosphane
2304-6740
Fortune, Kevin M.
67a13a74-0bd3-4857-af05-1287465d05e7
Castel, Christa
1be889bc-2ebc-4c91-9a99-5091a2f6b92b
Robertson, Craig M.
d08100a1-93ec-4503-86fd-1bdc9f0b1934
Horton, Peter
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Waugh, Mark
01be76cc-a778-45f8-8a64-80f1a1da7606
Clegg, William
5b1994af-8799-4402-9c01-8479959de00b
Harrington, Ross W.
01d1f0bc-fc3e-43ae-a087-6cce0278128e
Fortune, Kevin M.
67a13a74-0bd3-4857-af05-1287465d05e7
Castel, Christa
1be889bc-2ebc-4c91-9a99-5091a2f6b92b
Robertson, Craig M.
d08100a1-93ec-4503-86fd-1bdc9f0b1934
Horton, Peter
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Waugh, Mark
01be76cc-a778-45f8-8a64-80f1a1da7606
Clegg, William
5b1994af-8799-4402-9c01-8479959de00b
Harrington, Ross W.
01d1f0bc-fc3e-43ae-a087-6cce0278128e

Fortune, Kevin M., Castel, Christa, Robertson, Craig M., Horton, Peter, Light, Mark, Coles, Simon J., Waugh, Mark, Clegg, William and Harrington, Ross W. (2021) Ferrocenylmethylphosphanes and the alpha process for Methoxycarbonylation: The Original Story. Inorganics, 9 (7), [57]. (doi:10.3390/inorganics9070057).

Record type: Article

Abstract

The Lucite Alpha process is the predominant technology for the preparation of acrylics. This two-stage process involves the palladium-catalysed formation of methyl propanoate from ethene, CO, and methanol, followed by the oxidative formylation of methyl propanoate into methyl methacrylate. A range of bis-1,2-disubstituted aminomethylferrocenes has been prepared and characterised. These complexes serve as precursors to a variety of bulky ferrocenylmethyldiphosphanes that, in turn, function as ligands in the palladium-catalysed process. We describe the crystal structures of five ligand precursors and provide a rationale for their design. In situ catalyst testing on palladium complexes derived from ferrocenylphosphanes demonstrates that these are highly selective (>99.5%) catalysts for the formation of methyl propanoate from ethene, CO, and methanol and have turnover numbers exceeding 50,000. This article credits those researchers who worked on this project in the early days, who received little or no credit for their achievements and endeavours.

Text
inorganics-09-00057-v3 - Version of Record
Available under License Creative Commons Attribution.
Download (9MB)

More information

Accepted/In Press date: 14 July 2021
Published date: July 2021
Keywords: Catalysis, Ferrocene, Ligand, Methoxycarbonylation, Palladium, Phosphane

Identifiers

Local EPrints ID: 450735
URI: http://eprints.soton.ac.uk/id/eprint/450735
ISSN: 2304-6740
PURE UUID: 706feeac-c8a3-454b-9460-7e3a30a2327f
ORCID for Peter Horton: ORCID iD orcid.org/0000-0001-8886-2016
ORCID for Mark Light: ORCID iD orcid.org/0000-0002-0585-0843
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 09 Aug 2021 16:32
Last modified: 17 Mar 2024 02:50

Export record

Altmetrics

Contributors

Author: Kevin M. Fortune
Author: Christa Castel
Author: Craig M. Robertson
Author: Peter Horton ORCID iD
Author: Mark Light ORCID iD
Author: Simon J. Coles ORCID iD
Author: Mark Waugh
Author: William Clegg
Author: Ross W. Harrington

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×