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.

Cite: Salnikov O.G. , Liu H-J. , Fedorov A. , Burueva D.B. , Kovtunov K.V. , Copéret C. , Koptyug I.V.
Pairwise hydrogen addition in the selective semihydrogenation of alkynes on silica-supported Cu catalysts
Chemical Science. 2017. V.8. N3. P.2426-2430. DOI: 10.1039/c6sc05276b WOS Scopus

Dates:

Accepted:	Dec 18, 2016
Published print:	Mar 1, 2017

Identifiers:

Web of science:	WOS:000395906900095
Scopus:	2-s2.0-85014199716

Citing:

DB	Citing
Scopus	30
Web of science	29

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