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Silylation of Aryl Chlorides by Bimetallic Catalysis of Palladium and Gold on Alloy Nanoparticles

机译:钯和金对合金纳米粒子的双金属催化剂甲硅烷基化芳基氯化物

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摘要

Supported palladium-gold alloy-catalyzed cross-coupling of aryl chlorides and hydrosilanes enabled the selective formation of aryl-silicon bonds. Whereas a monometallic palladium catalyst predominantly promoted the hydrodechlorination of aryl chlorides and gold nanoparticles showed no catalytic activity, gold-rich palladium-gold alloy nanoparticles efficiently catalyzed the title reaction to give arylsilanes with high selectivity. A wide array of aryl chlorides and hydrosilanes participated in the heterogeneously-catalyzed reaction to furnish the corresponding arylsilanes in 34-80% yields. A detailed mechanistic investigation revealed that palladium and gold atoms on the surface of alloy nanoparticles independently functioned as active sites for the formation of aryl nucleophiles and silyl electrophiles, respectively, which indicates that palladium and gold atoms on alloy nanoparticles work together to enable the selective formation of aryl-silicon bonds.
机译:支撑的钯金合金催化芳基氯化物和水硅烷的交联偶联使得选择性地形成芳基 - 硅键。 虽然单金属钯催化剂主要促进芳基氯化物的水二氢,但黄金纳米粒子没有催化活性,但富含富金钯 - 金合金纳米颗粒有效地催化标题反应,得到具有高选择性芳基硅烷的芳基硅烷。 各种芳基氯和氢硅烷参与了非均相催化的反应,以在34-80%的产率下提供相应的芳基硅烷。 详细的机械研究表明,合金纳米颗粒表面上的钯和金原子分别独立地用作形成芳基亲核试剂和甲硅烷基的活性位点,这表明合金纳米粒子上的钯和金原子在一起,以使得能够选择性地形成 芳基 - 硅键。

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