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Direct Evaluation of the Reactivity of Nonheme Iron(V)-Oxo Intermediates Toward Arenes. / Lyakin, Oleg Y.; Zima, Alexandra M.; Tkachenko, Nikolay V. et al.

In: ACS Catalysis, Vol. 8, No. 6, 01.06.2018, p. 5255-5260.

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

Harvard

Lyakin, OY, Zima, AM, Tkachenko, NV, Bryliakov, KP & Talsi, EP 2018, 'Direct Evaluation of the Reactivity of Nonheme Iron(V)-Oxo Intermediates Toward Arenes', ACS Catalysis, vol. 8, no. 6, pp. 5255-5260. https://doi.org/10.1021/acscatal.8b00661

APA

Lyakin, O. Y., Zima, A. M., Tkachenko, N. V., Bryliakov, K. P., & Talsi, E. P. (2018). Direct Evaluation of the Reactivity of Nonheme Iron(V)-Oxo Intermediates Toward Arenes. ACS Catalysis, 8(6), 5255-5260. https://doi.org/10.1021/acscatal.8b00661

Vancouver

Lyakin OY, Zima AM, Tkachenko NV, Bryliakov KP, Talsi EP. Direct Evaluation of the Reactivity of Nonheme Iron(V)-Oxo Intermediates Toward Arenes. ACS Catalysis. 2018 Jun 1;8(6):5255-5260. doi: 10.1021/acscatal.8b00661

Author

Lyakin, Oleg Y. ; Zima, Alexandra M. ; Tkachenko, Nikolay V. et al. / Direct Evaluation of the Reactivity of Nonheme Iron(V)-Oxo Intermediates Toward Arenes. In: ACS Catalysis. 2018 ; Vol. 8, No. 6. pp. 5255-5260.

BibTeX

@article{20858c75255c46a583049fa05291c410,
title = "Direct Evaluation of the Reactivity of Nonheme Iron(V)-Oxo Intermediates Toward Arenes",
abstract = "The reactivity of nonheme iron(V)-oxo intermediates toward aromatic C-H oxidation at -70 °C has been directly evaluated. The intermediates were generated upon the interaction of the ferric complex [(PDP∗)FeIII(μ-OH)2FeIII(PDP∗)](OTf)4 (4- PDP∗ = N,N′-bis(3,5-dimethyl-4-methoxypyridyl-2-methyl)-(S,S)-2,2′-bipyrrolidine) with peracetic acid in the presence of acetic or 2-ethylhexanoic acid. The second-order rate constants (k2) for the reaction of substituted benzenes with iron-oxo intermediates [(PDP∗)FeV O(OC(O)R)]2+ at -70 °C were determined (R = CH3, 3-heptyl). For more electron rich arenes, much higher k2 values were observed, increasing in the order nitrobenzene < acetophenone < chlorobenzene < benzene < toluene, in accordance with the electrophilic aromatic substitution mechanism. The catalytic oxidation of mono- and dialkylbenzenes with H2O2 proceeded with good efficiency (up to 36.5 TN per Fe atom) and high selectivity toward aromatic oxidation products (up to 91%).",
keywords = "Aromatic C-H oxidation, enzyme models, EPR, iron, mechanism, aromatic C-H oxidation, COMPOUND-I, OXIDATION REACTIONS, MECHANISM, H2O2, OXYGEN-ACTIVATION, AROMATIC HYDROXYLATION, IRON(II) COMPLEXES, HYDROGEN-PEROXIDE, ELECTRONIC-STRUCTURE, BENZOIC-ACIDS",
author = "Lyakin, {Oleg Y.} and Zima, {Alexandra M.} and Tkachenko, {Nikolay V.} and Bryliakov, {Konstantin P.} and Talsi, {Evgenii P.}",
year = "2018",
month = jun,
day = "1",
doi = "10.1021/acscatal.8b00661",
language = "English",
volume = "8",
pages = "5255--5260",
journal = "ACS Catalysis",
issn = "2155-5435",
publisher = "American Chemical Society",
number = "6",

}

RIS

TY - JOUR

T1 - Direct Evaluation of the Reactivity of Nonheme Iron(V)-Oxo Intermediates Toward Arenes

AU - Lyakin, Oleg Y.

AU - Zima, Alexandra M.

AU - Tkachenko, Nikolay V.

AU - Bryliakov, Konstantin P.

AU - Talsi, Evgenii P.

PY - 2018/6/1

Y1 - 2018/6/1

N2 - The reactivity of nonheme iron(V)-oxo intermediates toward aromatic C-H oxidation at -70 °C has been directly evaluated. The intermediates were generated upon the interaction of the ferric complex [(PDP∗)FeIII(μ-OH)2FeIII(PDP∗)](OTf)4 (4- PDP∗ = N,N′-bis(3,5-dimethyl-4-methoxypyridyl-2-methyl)-(S,S)-2,2′-bipyrrolidine) with peracetic acid in the presence of acetic or 2-ethylhexanoic acid. The second-order rate constants (k2) for the reaction of substituted benzenes with iron-oxo intermediates [(PDP∗)FeV O(OC(O)R)]2+ at -70 °C were determined (R = CH3, 3-heptyl). For more electron rich arenes, much higher k2 values were observed, increasing in the order nitrobenzene < acetophenone < chlorobenzene < benzene < toluene, in accordance with the electrophilic aromatic substitution mechanism. The catalytic oxidation of mono- and dialkylbenzenes with H2O2 proceeded with good efficiency (up to 36.5 TN per Fe atom) and high selectivity toward aromatic oxidation products (up to 91%).

AB - The reactivity of nonheme iron(V)-oxo intermediates toward aromatic C-H oxidation at -70 °C has been directly evaluated. The intermediates were generated upon the interaction of the ferric complex [(PDP∗)FeIII(μ-OH)2FeIII(PDP∗)](OTf)4 (4- PDP∗ = N,N′-bis(3,5-dimethyl-4-methoxypyridyl-2-methyl)-(S,S)-2,2′-bipyrrolidine) with peracetic acid in the presence of acetic or 2-ethylhexanoic acid. The second-order rate constants (k2) for the reaction of substituted benzenes with iron-oxo intermediates [(PDP∗)FeV O(OC(O)R)]2+ at -70 °C were determined (R = CH3, 3-heptyl). For more electron rich arenes, much higher k2 values were observed, increasing in the order nitrobenzene < acetophenone < chlorobenzene < benzene < toluene, in accordance with the electrophilic aromatic substitution mechanism. The catalytic oxidation of mono- and dialkylbenzenes with H2O2 proceeded with good efficiency (up to 36.5 TN per Fe atom) and high selectivity toward aromatic oxidation products (up to 91%).

KW - Aromatic C-H oxidation

KW - enzyme models

KW - EPR

KW - iron

KW - mechanism

KW - aromatic C-H oxidation

KW - COMPOUND-I

KW - OXIDATION REACTIONS

KW - MECHANISM

KW - H2O2

KW - OXYGEN-ACTIVATION

KW - AROMATIC HYDROXYLATION

KW - IRON(II) COMPLEXES

KW - HYDROGEN-PEROXIDE

KW - ELECTRONIC-STRUCTURE

KW - BENZOIC-ACIDS

UR - http://www.scopus.com/inward/record.url?scp=85046545514&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/1b98188c-c4bf-3803-aec8-e5e6848e3eb3/

U2 - 10.1021/acscatal.8b00661

DO - 10.1021/acscatal.8b00661

M3 - Article

AN - SCOPUS:85046545514

VL - 8

SP - 5255

EP - 5260

JO - ACS Catalysis

JF - ACS Catalysis

SN - 2155-5435

IS - 6

ER -

ID: 13120739