Mechanistic Insight into Heterogeneous Hydrogenation of Furan Derivatives with the Use of Parahydrogen Full article
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ChemCatChem
ISSN: 1867-3880 , E-ISSN: 1867-3899 |
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| Output data | Year: 2018, Volume: 10, Number: 5, Pages: 1178-1183 Pages count : 6 DOI: 10.1002/cctc.201701653 | ||||||
| Tags | Hydrogenation, Oxygen heterocycles, Polarization, Reaction mechanisms, Supported catalysts | ||||||
| Authors |
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| Affiliations |
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Funding (4)
| 1 | Federal Agency for Scientific Organizations | 0303-2016-0004 |
| 2 | Russian Science Foundation | 17-73-20030 |
| 3 | Russian Foundation for Basic Research | 16-33-60198 |
| 4 | Federal Agency for Scientific Organizations | 0333-2017-0002 |
Abstract:
Parahydrogen-induced polarization (PHIP) was shown to be a useful and unique technique for mechanistic studies of catalytic reactions involving hydrogen. In this paper, PHIP was utilized for mechanistic investigation of gas phase hydrogenation of furan, 2,3-dihydrofuran and 2,5-dihydrofuran over titania-supported Rh, Pd and Pt catalysts. In hydrogenations of all three substrates over Rh/TiO2 catalysts, PHIP technique revealed the possibility of pairwise addition of two H atoms from the same H2 molecule with formation of tetrahydrofuran molecules while retaining spin correlation between added protons. In hydrogenation of 2,3-dihydrofuran over Rh/TiO2 catalysts, PHIP effects were detected not only for tetrahydrofuran but also for the reactant (2,3-dihydrofuran) at positions 2 and 3 of heterocyclic ring. Such unexpected results are a direct evidence of the occurrence of pairwise replacement of hydrogen atoms in 2,3-dihydorfuran. The probable mechanism of this pairwise replacement includes the sequential steps of addition and elimination of hydrogen atoms. In contrast, when hydrogenation of 2,5-dihydrofuran was carried out over Rh/TiO2, PHIP effects were detected for all protons of 2,3-dihydrofuran, implying that 2,3-dihydrofuran can be formed from 2,5-dihydrofuran not only via isomerization of C=C bond but also via dehydrogenation of 2,5-dihydrofuran to furan with subsequent semihydrogenation.
Cite:
Salnikov O.G.
, Kovtunova L.M.
, Skovpin I.V.
, Bukhtiyarov V.I.
, Kovtunov K.V.
, Koptyug I.V.
Mechanistic Insight into Heterogeneous Hydrogenation of Furan Derivatives with the Use of Parahydrogen
ChemCatChem. 2018. V.10. N5. P.1178-1183. DOI: 10.1002/cctc.201701653 WOS Scopus РИНЦ AN OpenAlex
Mechanistic Insight into Heterogeneous Hydrogenation of Furan Derivatives with the Use of Parahydrogen
ChemCatChem. 2018. V.10. N5. P.1178-1183. DOI: 10.1002/cctc.201701653 WOS Scopus РИНЦ AN OpenAlex
Dates:
| Submitted: | Oct 16, 2017 |
| Accepted: | Nov 7, 2017 |
| Published online: | Feb 5, 2018 |
| Published print: | Mar 7, 2018 |
Identifiers:
| Web of science: | WOS:000426844600042 |
| Scopus: | 2-s2.0-85041602872 |
| Elibrary: | 35514594 |
| Chemical Abstracts: | 2018:215396 |
| OpenAlex: | W2767252494 |