Additive-modulated switchable reaction pathway in the addition of alkynes with organosilanes catalyzed by supported Pd nanoparticles: hydrosilylation versus semihydrogenation

doi:10.1039/c7cy02280h

QIBEBT-IR

	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
发表期刊	CATALYSIS SCIENCE & TECHNOLOGY
ISSN	2044-4753
卷号	8 期号:4 页码:1039-1050
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.
文章类型	Article
WOS标题词	Science & Technology ; Physical Sciences
DOI	10.1039/c7cy02280h
关键词[WOS]	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
收录类别	SCI
语种	英语
WOS研究方向	Chemistry
项目资助者	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类目	Chemistry, Physical
WOS记录号	WOS:000427152800011
出版者	ROYAL SOC CHEMISTRY
引用统计	被引频次：32[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.qibebt.ac.cn/handle/337004/10682
专题	中国科学院青岛生物能源与过程研究所
通讯作者	Zhang, Shaochun; Yang, Yong
作者单位	Chinese Acad Sci, Qingdao Inst Bioenergy & Bioproc Technol, CAS Key Lab Biobased Mat, Qingdao 266101, Peoples R China
推荐引用方式 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.