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Direct reactivity studies of non-heme iron-oxo intermediates toward alkane oxidation. / Zima, Alexandra M.; Lyakin, Oleg Y.; Bryliakov, Konstantin P. et al.

In: Catalysis Communications, Vol. 108, 01.04.2018, p. 77-81.

Research output: Contribution to journal › Article › peer-review

Harvard

Zima, AM, Lyakin, OY, Bryliakov, KP & Talsi, EP 2018, 'Direct reactivity studies of non-heme iron-oxo intermediates toward alkane oxidation', Catalysis Communications, vol. 108, pp. 77-81. https://doi.org/10.1016/j.catcom.2018.01.034

APA

Zima, A. M., Lyakin, O. Y., Bryliakov, K. P., & Talsi, E. P. (2018). Direct reactivity studies of non-heme iron-oxo intermediates toward alkane oxidation. Catalysis Communications, 108, 77-81. https://doi.org/10.1016/j.catcom.2018.01.034

Vancouver

Zima AM, Lyakin OY, Bryliakov KP, Talsi EP. Direct reactivity studies of non-heme iron-oxo intermediates toward alkane oxidation. Catalysis Communications. 2018 Apr 1;108:77-81. doi: 10.1016/j.catcom.2018.01.034

Author

Zima, Alexandra M. ; Lyakin, Oleg Y. ; Bryliakov, Konstantin P. et al. / Direct reactivity studies of non-heme iron-oxo intermediates toward alkane oxidation. In: Catalysis Communications. 2018 ; Vol. 108. pp. 77-81.

BibTeX

@article{5b70a626f9ef47d98912ff3a20d66c8d,
title = "Direct reactivity studies of non-heme iron-oxo intermediates toward alkane oxidation",
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).",
keywords = "C–H oxidation, Enzyme models, EPR spectroscopy, Iron, Reaction mechanisms, ACTIVATION, ACTIVE-SITES, COMPLEXES, CATALYST, H2O2, C-H oxidation, ENZYMES, BONDS, C-H OXIDATION, SELECTIVITY, FE",
author = "Zima, {Alexandra M.} and Lyakin, {Oleg Y.} and Bryliakov, {Konstantin P.} and Talsi, {Evgenii P.}",
year = "2018",
month = apr,
day = "1",
doi = "10.1016/j.catcom.2018.01.034",
language = "English",
volume = "108",
pages = "77--81",
journal = "Catalysis Communications",
issn = "1566-7367",
publisher = "Elsevier",

}

RIS

TY - JOUR

T1 - Direct reactivity studies of non-heme iron-oxo intermediates toward alkane oxidation

AU - Zima, Alexandra M.

AU - Lyakin, Oleg Y.

AU - Bryliakov, Konstantin P.

AU - Talsi, Evgenii P.

PY - 2018/4/1

Y1 - 2018/4/1

N2 - 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).

AB - 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).

KW - C–H oxidation

KW - Enzyme models

KW - EPR spectroscopy

KW - Iron

KW - Reaction mechanisms

KW - ACTIVATION

KW - ACTIVE-SITES

KW - COMPLEXES

KW - CATALYST

KW - H2O2

KW - C-H oxidation

KW - ENZYMES

KW - BONDS

KW - C-H OXIDATION

KW - SELECTIVITY

KW - FE

UR - http://www.scopus.com/inward/record.url?scp=85041401940&partnerID=8YFLogxK

U2 - 10.1016/j.catcom.2018.01.034

DO - 10.1016/j.catcom.2018.01.034

M3 - Article

AN - SCOPUS:85041401940

VL - 108

SP - 77

EP - 81

JO - Catalysis Communications

JF - Catalysis Communications

SN - 1566-7367

ER -

ID: 9539641