Issue 3, 2017

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

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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
01 Dec 2016
Accepted
18 Dec 2016
First published
20 Dec 2016
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 2426-2430

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

O. G. Salnikov, H. Liu, A. Fedorov, D. B. Burueva, K. V. Kovtunov, C. Copéret and I. V. Koptyug, Chem. Sci., 2017, 8, 2426 DOI: 10.1039/C6SC05276B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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