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

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Pairwise hydrogen addition in the selective semihydrogenation of alkynes on silica-supported Cu catalysts. / Salnikov, Oleg G.; Liu, Hsueh Ju; Fedorov, Alexey et al.

In: Chemical Science, Vol. 8, No. 3, 01.03.2017, p. 2426-2430.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{41ae7cda741f4cbebaeac2507ec35e2c,

title = "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.",

keywords = "ADSORPTION, DNP, DYNAMIC NUCLEAR-POLARIZATION, ENHANCED NMR-SPECTROSCOPY, HETEROGENEOUS HYDROGENATION, HYPERPOLARIZATION, ION-EXCHANGED COPPER, PARAHYDROGEN-INDUCED POLARIZATION, PROPYNE, STATE NMR",

author = "Salnikov, {Oleg G.} and Liu, {Hsueh Ju} and Alexey Fedorov and Burueva, {Dudari B.} and Kovtunov, {Kirill V.} and Christophe Cop{\'e}ret and Koptyug, {Igor V.}",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry.",

year = "2017",

month = mar,

day = "1",

doi = "10.1039/c6sc05276b",

language = "English",

volume = "8",

pages = "2426--2430",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "3",

}

RIS

TY - JOUR

T1 - Pairwise hydrogen addition in the selective semihydrogenation of alkynes on silica-supported Cu catalysts

AU - Salnikov, Oleg G.

AU - Liu, Hsueh Ju

AU - Fedorov, Alexey

AU - Burueva, Dudari B.

AU - Kovtunov, Kirill V.

AU - Copéret, Christophe

AU - Koptyug, Igor V.

N1 - Publisher Copyright: © The Royal Society of Chemistry.

PY - 2017/3/1

Y1 - 2017/3/1

N2 - 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.

AB - 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.

KW - ADSORPTION

KW - DNP

KW - DYNAMIC NUCLEAR-POLARIZATION

KW - ENHANCED NMR-SPECTROSCOPY

KW - HETEROGENEOUS HYDROGENATION

KW - HYPERPOLARIZATION

KW - ION-EXCHANGED COPPER

KW - PARAHYDROGEN-INDUCED POLARIZATION

KW - PROPYNE

KW - STATE NMR

UR - http://www.scopus.com/inward/record.url?scp=85014199716&partnerID=8YFLogxK

U2 - 10.1039/c6sc05276b

DO - 10.1039/c6sc05276b

M3 - Article

C2 - 28451349

AN - SCOPUS:85014199716

VL - 8

SP - 2426

EP - 2430

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 3

ER -

ID: 10278152