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首页> 外文期刊>Catalysis science & technology >Additive-modulated switchable reaction pathway in the addition of alkynes with organosilanes catalyzed by supported Pd nanoparticles: hydrosilylation versus semihydrogenation
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Additive-modulated switchable reaction pathway in the addition of alkynes with organosilanes catalyzed by supported Pd nanoparticles: hydrosilylation versus semihydrogenation

机译：Additive-modulated可切换的反应途径与有机硅烷的炔烃通过支持钯纳米颗粒催化:氢化硅烷化和semihydrogenation

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摘要

We herein report supported Pd nanoparticles on N,O-doped hierarchical porous carbon as a single operation catalyst-enabled additive-modulated reaction pathway for alkynes addition with organosilanes between hydrosilyation and semihydrogenation. In the case of alkynes hydrosilylation, a simple iodide ion as an additive has a promotion effect on the activity and regio- and stereoselectivity, where iodide can coordinate with Pd NPs via strong delta donation to increase the electron density of the Pd atom, resulting in an increased ability for the oxidative addition of hydrosilane as the rate-determining step to make the reaction proceed efficiently to afford vinylsilanes in high yields with excellent regio-and stereoselectivity. For the catalytic transfer semihydrogenation of alkynes, water was introduced to mix with organosilane to form a silanol together with the generation of hydrogen atoms on the Pd NPs surface or the liberation of H-2 gas as a reducing agent, whereby the quantitative reduction of alkynes was achieved with exclusive selectivity to alkenes. In both cases, the catalyst could be recycled several times without a significant loss in activity or selectivity. A broad range of alkyl and aryl alkynes with various functional groups are compatible with the reaction conditions. The role the additive exerted in each reaction was extensively investigated through control experiments as well as the kinetic isotopic effect along with spectroscopic characterization. In addition, the respective mechanism operating in both reactions was proposed.
机译：我们在此报告支持Pd纳米颗粒N, O-doped分级多孔碳作为一个单独的操作帖催化剂使additive-modulated炔烃加法的反应途径有机硅烷和hydrosilyation之间semihydrogenation。氢化硅烷化,一个简单的碘离子作为一个添加剂有促销活动和地区,立体选择性,碘化可以通过强大的三角洲与Pd NPs协调吗捐款增加的电子密度钯原子,导致增加能力hydrosilane的氧化加成速率决定步骤做出反应进行有效地承受多regio-and的高收益立体选择性。semihydrogenation炔烃、水介绍了与有机硅烷混合形成硅醇与氢的生成Pd NPs表面原子或解放2气体作为还原剂,即量化减少炔烃独家烯烃选择性。情况下,催化剂可以回收一些次没有活动或重大损失选择性。炔烃与各种官能团与反应条件兼容。在每个反应是添加剂产生通过控制广泛的调查实验以及动力学同位素随着光谱特性的影响。此外,相应的操作机制提出了两种反应。

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