Ethylene Carbonylation in Methanol and in Aqueous Media by Palladium(II) Catalysts Modified with 1,1'-Bis(dialkylphosphino)ferrocenes

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• 作者：Claudio Bianchini ; Andrea Meli ; Werner Oberhauser ; Sebastien Parisel ; Elisa Passaglia ; Francesco Ciardelli ; Oleg V. Gusev ; Alexander M. Kal'sin ; and Nikolai V. Vologdin
• 刊名：Organometallics
• 出版年：2005
• 出版时间：February 28, 2005
• 年：2005
• 卷：24
• 期：5
• 页码：1018 - 1030
• 全文大小：244K
• 年卷期：v.24,no.5(February 28, 2005)
• ISSN：1520-6041

文摘

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 thecarbonylation 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 dippfcatalyst. The last catalyst was inactive in aqueous solvent. In contrast, the dmpf and depfcatalysts were active in either water or water/1,4-dioxane for the copolymerization of COwith ethylene. These two catalysts were efficient also for the terpolymerization of CO withethylene and propene in MeOH or water/1,4-dioxane. Operando high-pressure NMRexperiments and in situ reactions with model compounds have provided useful informationto rationalize the activity and selectivity of the catalytic systems investigated.