Nanoparticulate palladium supported by covalently modified silicas: Synthesis, characterization, and application as catalysts for the Suzuki coupling of aryl halides

被引:120
作者
Bedford, RB
Singh, UG
Walton, RI
Williams, RT
Davis, SA
机构
[1] Univ Exeter, Dept Chem, Exeter EX4 4QD, Devon, England
[2] Open Univ, Dept Chem, Milton Keynes MK7 6AA, Bucks, England
[3] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England
关键词
D O I
10.1021/cm048860s
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We present a study of the use of amine-functionalized, mesoporous silicas as supports for nanoparticulate palladium, and the use of the composite materials as heterogeneous catalysts for the Suzuki coupling of aryl bromides. Upon modification of the silica, via attachment of N-functionalized aminopropylsilyl ethers to surface silanol groups, only a small reduction in surface area and average pore diameter is observed. The mesoporosity and high surface area are also maintained after introduction of nanoparticulate palladium, as evidenced by the measurement of BET nitrogen sorption isotherms. Electron microscopy shows that the palladium particles are well-dispersed and of typical diameter 3-6 nm. Catalysis was initially tested using the coupling of phenylboronic acid with 4-bromoanisole in the presence of K2CO3 and with toluene as solvent. This revealed that the choice of organic modification has a crucial role in determining the activity and recyclability of the catalyst: optimum behavior was found for diamine- and triamine-containing systems, while quaternary alkylammonium salts showed poor activities. The optimized catalysts are also active in the coupling of a range of aryl bromides and phenylboronic acids, and after three catalytic runs they show virtually no drop in activity. Upon further cycling, however, and after six catalytic runs, we do observe a drop in activity, and this is accompanied by some leaching of palladium and pore-blocking by reaction products and byproducts.
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页码:701 / 707
页数:7
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