Direct reactivity studies of non-heme iron-oxo intermediates toward alkane oxidation

Результат исследования: Научные публикации в периодических изданияхстатья

11 Цитирования (Scopus)

Аннотация

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).

Язык оригиналаанглийский
Страницы (с-по)77-81
Число страниц5
ЖурналCatalysis Communications
Том108
DOI
СостояниеОпубликовано - 1 апр 2018

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