Ethylene Carbonylation in Methanol and in Aqueous Media by Palladium(II) Catalysts Modified with 1,1‘-Bis(dialkylphosphino)ferrocenes
Palladium(II) complexes with the formula [Pd(H2O)(OTs)(P-P)]OTs, where P-P is 1,1‘-bis(dimethylphosphino)ferrocene (dmpf), 1,1‘-bis(diethylphosphino)ferrocene (depf), or 1,1‘-bis(diisopropylphosphino)ferrocene (dippf), have been synthesized and used to catalyze the carbonylation of ethylene in MeOH,...
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Veröffentlicht in: | Organometallics 2005-02, Vol.24 (5), p.1018-1030 |
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Hauptverfasser: | , , , , , , , , |
Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | Palladium(II) complexes with the formula [Pd(H2O)(OTs)(P-P)]OTs, where P-P is 1,1‘-bis(dimethylphosphino)ferrocene (dmpf), 1,1‘-bis(diethylphosphino)ferrocene (depf), or 1,1‘-bis(diisopropylphosphino)ferrocene (dippf), have been synthesized and used to catalyze the carbonylation of ethylene in MeOH, water, or a 1/1 water/1,4-dioxane mixture. In MeOH, the reactions catalyzed by the dmpf and depf complexes gave alternating polyketone (alt-E-CO), while methyl propanoate and 3-pentanone were selectively produced with the dippf catalyst. The last catalyst was inactive in aqueous solvent. In contrast, the dmpf and depf catalysts were active in either water or water/1,4-dioxane for the copolymerization of CO with ethylene. These two catalysts were efficient also for the terpolymerization of CO with ethylene and propene in MeOH or water/1,4-dioxane. Operando high-pressure NMR experiments and in situ reactions with model compounds have provided useful information to rationalize the activity and selectivity of the catalytic systems investigated. |
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ISSN: | 0276-7333 1520-6041 |
DOI: | 10.1021/om049109w |