KMS Qingdao Institute of Biomass Energy and Bioprocess Technology ,CAS
| Additive-modulated switchable reaction pathway in the addition of alkynes with organosilanes catalyzed by supported Pd nanoparticles: hydrosilylation versus semihydrogenation | |
| Duan, Yanan; Ji, Guijie; Zhang, Shaochun; Chen, Xiufang; Yang, Yong | |
| 2018-02-21 | |
| Source Publication | CATALYSIS SCIENCE & TECHNOLOGY
 |
| ISSN | 2044-4753 |
| Volume | 8Issue:4Pages:1039-1050 |
| Abstract | 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. |
| Subtype | Article |
| WOS Headings | Science & Technology ; Physical Sciences |
| DOI | 10.1039/c7cy02280h |
| WOS Keyword | HIGHLY SELECTIVE SEMIHYDROGENATION ; CARBENE PLATINUM(0) COMPLEXES ; N-HETEROCYCLIC CARBENES ; CARBON MULTIPLE BONDS ; 8 METAL COMPLEXES ; STEREOSELECTIVE HYDROSILYLATION ; TERMINAL ALKYNES ; INTERNAL ALKYNES ; RUTHENIUM COMPLEXES ; CIS-ALKENES |
| Indexed By | SCI |
| Language | 英语 |
| WOS Research Area | Chemistry |
| Funding Organization | Qingdao Institute of Bioenergy and Bioprocess Technology (QIBEBT) ; Chinese Academy of Sciences(Y6710619KL) ; 13th-Five Key Project of the Chinese Academy of Sciences(Y7720519KL) |
| WOS Subject | Chemistry, Physical |
| WOS ID | WOS:000427152800011 |
| Publisher | ROYAL SOC CHEMISTRY |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.qibebt.ac.cn/handle/337004/10682 |
| Collection | 中国科学院青岛生物能源与过程研究所 |
| Corresponding Author | Zhang, Shaochun; Yang, Yong |
| Affiliation | Chinese Acad Sci, Qingdao Inst Bioenergy & Bioproc Technol, CAS Key Lab Biobased Mat, Qingdao 266101, Peoples R China |
| Recommended Citation GB/T 7714 | Duan, Yanan,Ji, Guijie,Zhang, Shaochun,et al. Additive-modulated switchable reaction pathway in the addition of alkynes with organosilanes catalyzed by supported Pd nanoparticles: hydrosilylation versus semihydrogenation[J]. CATALYSIS SCIENCE & TECHNOLOGY,2018,8(4):1039-1050. |
| APA | Duan, Yanan,Ji, Guijie,Zhang, Shaochun,Chen, Xiufang,&Yang, Yong.(2018).Additive-modulated switchable reaction pathway in the addition of alkynes with organosilanes catalyzed by supported Pd nanoparticles: hydrosilylation versus semihydrogenation.CATALYSIS SCIENCE & TECHNOLOGY,8(4),1039-1050. |
| MLA | Duan, Yanan,et al."Additive-modulated switchable reaction pathway in the addition of alkynes with organosilanes catalyzed by supported Pd nanoparticles: hydrosilylation versus semihydrogenation".CATALYSIS SCIENCE & TECHNOLOGY 8.4(2018):1039-1050. |
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