TY - JOUR

T1 - Ferrocenylmethylphosphanes and the Alpha Process for Methoxycarbonylation: The Original Story

AU - Fortune, Kevin M.

AU - Castel, Christa

AU - Robertson, Craig M.

AU - Horton, Peter N.

AU - Light, Mark E.

AU - Coles, Simon J.

AU - Waugh, Mark

AU - Clegg, William

AU - Harrington, Ross W.

AU - Butler, Ian R.

PY - 2021/7/17

Y1 - 2021/7/17

N2 - 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.

AB - 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.

U2 - 10.3390/inorganics9070057

DO - 10.3390/inorganics9070057

M3 - Article

VL - 9

JO - Inorganics

JF - Inorganics

SN - 2304-6740

IS - 7

M1 - 57

ER -