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Additive-Modulated Switchable Reaction Pathway in the Addition of Alkynes with Organosilanes Catalyzed by a Supported Pd Nanoparticles: Hydrosilylation versus Semihydrogenation

Abstract

We herein report a single operation supported Pd nanoparticles on N,O-doped hierarchical porous carbon 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 additive plays a promoted effect on activity, regio- and stereoselectivity, where iodide can coordinate with Pd NPs via strong δ donation to increase electron density of Pd atom, resulting in an increased ability for 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 catalytic transfer semihydrogenation of alkynes, water was introduced to mix with organosilane to form silanol together with generation of hydrogen atom on Pd NPs surface or liberation of H2 gas as reducing agent, quantitative reduction of alkynes was achieved with exclusive selectivity to alkenes. In both cases, the catalyst can be recycled several times without significant loss in activity and selectivity. A broad range of alkyl and aryl alkynes with various functional groups is compatible with the reaction conditions. The role of the additive exerted in each reaction was extensively investigated through control experiments and kinetic isotopic effect along with spectroscopic characterization. In addition, the respective mechanism operated in both reactions was proposed.

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Publication details

The article was received on 07 Nov 2017, accepted on 27 Nov 2017 and first published on 30 Nov 2017


Article type: Paper
DOI: 10.1039/C7CY02280H
Citation: Catal. Sci. Technol., 2017, Accepted Manuscript
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    Additive-Modulated Switchable Reaction Pathway in the Addition of Alkynes with Organosilanes Catalyzed by a Supported Pd Nanoparticles: Hydrosilylation versus Semihydrogenation

    Y. Duan, G. Ji, S. Zhang, X. Chen and Y. Yang, Catal. Sci. Technol., 2017, Accepted Manuscript , DOI: 10.1039/C7CY02280H

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