期刊
ORGANOMETALLICS
卷 34, 期 12, 页码 3021-3028出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.5b00322
关键词
-
资金
- Natural Sciences and Engineering Research Council (NSERC) of Canada
- Canada Foundation for Innovation (CFI)
- British Columbia Knowledge Development Fund (BCKDF)
- University of Victoria
- EPSRC [EP/J02127X/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/J02127X/1] Funding Source: researchfish
The cationic rhodium complex [Rh((PPr3)-Pr-c)(2)(eta(6)-PhF)](+)[B{3,5-(CF3)(2)C6H3}(4)](-) ((PPr3)-Pr-c = triscyclopropylphosphine, PhF = fluorobenzene) was used as a catalyst for the hydrogenation of the charge-tagged alkyne [Ph3P(CH2)(4)C2H](+)[PF6](-). Pressurized sample infusion electrospray ionization mass spectrometry (PSI-ESI-MS) was used to monitor reaction progress. Experiments revealed that the reaction is first order in catalyst and first order in hydrogen, so under conditions of excess hydrogen the reaction is pseudo-zero order. Alkyne hydrogenation was 40 times faster than alkene hydrogenation. The turnover-limiting step is proposed to be oxidative addition of hydrogen to the alkyne (or alkene)-bound complex. Addition of triethylamine caused a dramatic reduction in rate, suggesting a deprotonation pathway was not operative.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据