EPR and DFT Study of the Ethylene Reaction with O− Radicals on the Surface of Nanocrystalline MgO Full article
| Journal |
Research on Chemical Intermediates
ISSN: 0922-6168 , E-ISSN: 1568-5675 |
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| Output data | Year: 2017, Volume: 43, Number: 2, Pages: 1047-1061 Pages count : 15 DOI: 10.1007/s11164-016-2682-9 | ||||
| Tags | DFT, EPR, Ethylene, MgO, O− radicals | ||||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | Russian Foundation for Basic Research | 15-03-08070 |
| 2 | Russian Foundation for Basic Research | 14-03-01110 |
Abstract:
Different radical forms of oxygen (O−, O 2 − and O 3 − ) on the surface of nanocrystalline MgO are well known. It was earlier demonstrated that EPR-silent species with properties very similar to those of O− radicals exist on the surface of magnesium oxide in addition to the O− radicals observed by EPR. In this study we characterized the reactivity of these two types of O− radicals in reaction with ethylene. It was demonstrated that this reaction yields different products for observable and unobservable O− radicals. Conventional O−3CO3C− radicals generated by MgO illumination with UV light at room temperature in the presence of oxygen initiate hydrogen atom abstraction from ethylene to form secondary radicals H2C=C− with hyperfine splitting A 1 = 59 G, A 2 = 6 G. The O−4CO4C− radicals not observed directly by EPR were synthesized by MgO illumination in the presence of oxygen at 163 K followed by evacuation at 203 K. They were shown to react with ethylene to form an addition product with two groups of two equivalent protons with isotropic hyperfine constants A 1 = 38 G and A 2 = 23 G. Such radicals were obtained for the first time by reaction of O− radicals with ethylene on the MgO surface. Their concentration was approximately equal to the concentration of [O−4CO4C−·O2] complexes observed by EPR before the oxygen desorption. The structures of both radicals were simulated by DFT, and a good match between the experimental and computational results was obtained.
Cite:
Volodin A.M.
, Avdeev V.I.
, Malykhin S.E.
, Bedilo A.F.
EPR and DFT Study of the Ethylene Reaction with O− Radicals on the Surface of Nanocrystalline MgO
Research on Chemical Intermediates. 2017. V.43. N2. P.1047-1061. DOI: 10.1007/s11164-016-2682-9 WOS Scopus РИНЦ ANCAN OpenAlex
EPR and DFT Study of the Ethylene Reaction with O− Radicals on the Surface of Nanocrystalline MgO
Research on Chemical Intermediates. 2017. V.43. N2. P.1047-1061. DOI: 10.1007/s11164-016-2682-9 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
| Submitted: | Jun 10, 2016 |
| Accepted: | Jul 19, 2016 |
| Published online: | Aug 12, 2016 |
| Published print: | Feb 1, 2017 |
Identifiers:
| Web of science: | WOS:000394374300031 |
| Scopus: | 2-s2.0-84982099151 |
| Elibrary: | 29464983 |
| Chemical Abstracts: | 2016:1348878 |
| Chemical Abstracts (print): | 166:165526 |
| OpenAlex: | W2512109274 |