Direct Reactivity Studies of Non-Heme Iron-Oxo Intermediates Toward Alkane Oxidation Full article
| Journal |
Catalysis Communications
ISSN: 1566-7367 , E-ISSN: 1873-3905 |
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| Output data | Year: 2018, Volume: 108, Pages: 77-81 Pages count : 5 DOI: 10.1016/j.catcom.2018.01.034 | ||||
| Tags | C–H oxidation, Enzyme models, EPR spectroscopy, Iron, Reaction mechanisms | ||||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | Russian Foundation for Basic Research | 17-03-00991 |
| 2 | Federal Agency for Scientific Organizations | 0303-2016-0005 |
Abstract:
Iron complexes [((S,S)-PDP*)FeIII(μ-OH)2FeIII((S,S)-PDP*)](OTf)4 (6), (S,S)-PDP* = N,N′-bis(3,5-dimethyl-4-methoxypyridyl-2-methyl)-(S,S)-2,2′-bipyrrolidine, and [(TPA*)FeIII(μ-OH)2FeIII(TPA*)](OTf)4 (7), TPA* = tris(3,5-dimethyl-4-methoxypyridyl-2-methyl)amine, catalyze the selective hydroxylation of alkanes with H2O2 and peroxycarboxylic acids. Using in situ EPR spectroscopy, direct kinetic data on the reactivity of the iron-oxo intermediates formed in the catalyst systems 6,7/oxidant/RCOOH (RCOOH = acetic acid (AA) or 2-ethylhexanoic acid (EHA)) toward cyclohexane have been obtained for the first time, thus corroborating their key role in the selective C–H oxidation. Intermediates 6aAA, 6aEHA and 7a2 EHA with proposed structures [((S,S)-PDP*)FeV[dbnd]O(OC(O)CH3)]2+, [((S,S)-PDP*)FeV[dbnd]O(OC(O)R)]2+ and [(TPA*)FeV[dbnd]O(OC(O)R)]2+ (RCOOH = EHA) display similar EPR spectra (g1 = 2.07, g2 = 2.01, g3 = 1.96) and have close reactivities toward cyclohexane at −70 °C (k2 = 2–3 × 10−3 M−1 s−1).
Cite:
Zima A.M.
, Lyakin O.Y.
, Bryliakov K.P.
, Talsi E.P.
Direct Reactivity Studies of Non-Heme Iron-Oxo Intermediates Toward Alkane Oxidation
Catalysis Communications. 2018. V.108. P.77-81. DOI: 10.1016/j.catcom.2018.01.034 WOS Scopus РИНЦ OpenAlex AN
Direct Reactivity Studies of Non-Heme Iron-Oxo Intermediates Toward Alkane Oxidation
Catalysis Communications. 2018. V.108. P.77-81. DOI: 10.1016/j.catcom.2018.01.034 WOS Scopus РИНЦ OpenAlex AN
Dates:
| Submitted: | Dec 6, 2017 |
| Accepted: | Jan 31, 2018 |
| Published online: | Feb 2, 2018 |
| Published print: | Apr 1, 2018 |
Identifiers:
| ≡ Web of science: | WOS:000432766800016 |
| ≡ Scopus: | 2-s2.0-85041401940 |
| ≡ Elibrary: | 35484681 |
| ≡ OpenAlex: | W2793117617 |
| ≡ Chemical Abstracts: | 2018:259966 |