Pairwise hydrogen addition in the selective semihydrogenation of alkynes on silica-supported Cu catalysts

Open access
Author
Show all
Date
2017-03-01Type
- Journal Article
Citations
Cited null times in
Web of Science
Cited 15 times in
Scopus
ETH Bibliography
yes
Altmetrics
Abstract
Mechanistic insight into the semihydrogenation of 1-butyne and 2-butyne on Cu nanoparticles supported on partially dehydroxylated silica (Cu/SiO2-700) was obtained using parahydrogen. Hydrogenation of 1-butyne over Cu/SiO2-700 yielded 1-butene with ≥97% selectivity. The surface modification of this catalyst with tricyclohexylphosphine (PCy3) increased the selectivity to 1-butene up to nearly 100%, although at the expense of reduced catalytic activity. Similar trends were observed in the hydrogenation of 2-butyne, where Cu/SiO2-700 provided a selectivity to 2-butene in the range of 72–100% depending on the reaction conditions, while the catalyst modified with PCy3 again demonstrated nearly 100% selectivity. Parahydrogen-induced polarization effects observed in hydrogenation reactions catalyzed by copper-based catalysts demonstrate the viability of pairwise hydrogen addition over these catalysts. Contribution of pairwise hydrogen addition to 1-butyne was estimated to be at least 0.2–0.6% for unmodified Cu/SiO2-700 and ≥2.7% for Cu/SiO2-700 modified with PCy3, highlighting the effect of surface modification with the tricyclohexylphosphine ligand. Show more
Permanent link
https://doi.org/10.3929/ethz-b-000129486Publication status
publishedExternal links
Journal / series
Chemical ScienceVolume
Pages / Article No.
Publisher
Royal Society of ChemistryOrganisational unit
03872 - Copéret, Christophe / Copéret, Christophe
More
Show all metadata
Citations
Cited null times in
Web of Science
Cited 15 times in
Scopus
ETH Bibliography
yes
Altmetrics