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Direct Reactivity Studies of Non-Heme Iron-Oxo Intermediates Toward Alkane Oxidation Full article

Journal Catalysis Communications
ISSN: 1566-7367 , E-ISSN: 1873-3905
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 Zima Alexandra M. 1,2 , Lyakin Oleg Y. 1,2 , Bryliakov Konstantin P. 1,2 , Talsi Evgenii P. 1,2
Affiliations
1 Novosibirsk State University, Pirogova 2, Novosibirsk 630090, Russian Federation
2 Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russian Federation

Funding (2)

1 Federal Agency for Scientific Organizations 0303-2016-0005
2 Russian Foundation for Basic Research 17-03-00991

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 AN OpenAlex
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
Chemical Abstracts: 2018:259966
OpenAlex: W2793117617
Citing:
DB Citing
Web of science 17
Scopus 17
Elibrary 17
OpenAlex 17
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