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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.
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Castel, Christa
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Robertson, Craig M.
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Horton, Peter
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Light, Mark
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Coles, Simon J.
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Waugh, Mark
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Clegg, William
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Harrington, Ross W.
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Fortune, Kevin M.
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Castel, Christa
1be889bc-2ebc-4c91-9a99-5091a2f6b92b
Robertson, Craig M.
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Horton, Peter
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
Coles, Simon J.
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Waugh, Mark
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Clegg, William
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Harrington, Ross W.
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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.

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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: 26 Nov 2021 02:43

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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

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