“…However, this is the story of the ligands' synthetic development and use. This work brings together these reports [1][2][3][4][5] and adds previously unpublished material.…”
Section: Introductionsupporting
confidence: 53%
“…This work remained unpublished because of circumstances prevalent at the time of completion. There have been some work presentations; we published two short communications on ligand synthesis [4,5]. However, this is the story of the ligands' synthetic development and use.…”
Section: Introductionmentioning
confidence: 99%
“…Our group pioneered the preparation of ferrocene-based ligands for the methoxycarbonylation reaction of ethene, and we previously described the synthesis of ferrocenebased ligands-such as compound 2-that are similar in structure to the Alpha ligand, compound 1 [5,6]. Butler and Greenwell developed the ligand synthesis in 1998, and the work was further developed by Fortune in a programme partially funded by IN-EOS Acrylics/Lucite International.…”
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.
“…However, this is the story of the ligands' synthetic development and use. This work brings together these reports [1][2][3][4][5] and adds previously unpublished material.…”
Section: Introductionsupporting
confidence: 53%
“…This work remained unpublished because of circumstances prevalent at the time of completion. There have been some work presentations; we published two short communications on ligand synthesis [4,5]. However, this is the story of the ligands' synthetic development and use.…”
Section: Introductionmentioning
confidence: 99%
“…Our group pioneered the preparation of ferrocene-based ligands for the methoxycarbonylation reaction of ethene, and we previously described the synthesis of ferrocenebased ligands-such as compound 2-that are similar in structure to the Alpha ligand, compound 1 [5,6]. Butler and Greenwell developed the ligand synthesis in 1998, and the work was further developed by Fortune in a programme partially funded by IN-EOS Acrylics/Lucite International.…”
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.
“…The dippf-, dppomf- and dppo-based catalysts are moderately active (TOF MP = 300–400 h −1 under typical carbonylation conditions (85 °C, 40 bar, CO:ethane = 1:1). A much higher performant catalyst is the one with the sterically hindered ligand 11 in Figure 2 [72]. With an excess of ligand and ethene (Pd:ligand = 1:5.3, ethane:CO = 9:1) at 100 °C and 10 bar, typical TON were 59,000–64,000, with initial TOF of 30,000–31,000 h −1 [73].…”
Section: Influence Of the Ligand On The Product Formationmentioning
This review deals with olefin carbonylation catalysed by Pd(II)-phosphine complexes in protic solvents. In particular, the results obtained in the carbonylation with ethene are reviewed. After a short description of the basic concepts relevant to this catalysis, the review treats in greater details the influence of the bite angle, skeletal rigidity, electronic and steric bulk properties of the ligand on the formation of the products, which range from high molecular weight perfectly alternating polyketones to methyl propanoate. It is shown that the steric bulk plays a major role in directing the selectivity. Particular emphasis is given to the factors governing the very active and selective catalysis to methyl propanoate, including the mechanism of the catalytic cycles with diphosphine-and monophosphine-catalysts. A brief note on the synthesis of methyl propanoate using a "Lucite" type catalyst in ionic liquids is also illustrated. A chapter is dedicated to the carbonylation of olefins in aqueous reaction media. The nonalternating CO-ethene copolymerization is also treated.
“…52,000). In conclusion the new ferrocenylmethylphosphanes are described using a new synthetic procedure and are extremely promising candidates for industrial application [12].…”
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