Effect of different carboxylic acids on the aromatic hydroxylation with H2O2 in the presence of an iron aminopyridine complex

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Effect of different carboxylic acids on the aromatic hydroxylation with H₂O₂ in the presence of an iron aminopyridine complex. / Tkachenko, Nikolay V.; Lyakin, Oleg Y.; Zima, Alexandra M. et al.

In: Journal of Organometallic Chemistry, Vol. 871, 15.09.2018, p. 130-134.

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

BibTeX

@article{f02def1330854fe5b3425aff0ee4ef4b,

title = "Effect of different carboxylic acids on the aromatic hydroxylation with H2O2 in the presence of an iron aminopyridine complex",

abstract = "In this contribution, the effect of the structure of the catalytic additive – carboxylic acid – on the catalytic performance of the iron based catalyst [(PDP)Fe(OTf)2], 2 (PDP = N,N′-bis(2-pyridylmethyl)-(S,S)-2,2′-bipyrrolidine) in the selective aromatic oxidation of alkylbenzenes with H2O2 is presented. Eight (linear and branched) carboxylic acids have been tested; in the presence of 2-ethylhexanoic acid, the system [(PDP)Fe(OTf)2]/RCOOH/H2O2 has demonstrated the highest substrate conversion and the highest selectivity for oxygen incorporation into the aromatic ring (up to > 99%) at the same time. Low-temperature EPR spectroscopic study of the system [(PDP)Fe(OTf)2]/2-ethylhexanoic acid/H2O2 witness the presence of the low-spin perferryl intermediate 2aEHA with small g-factor anisotropy (g1 = 2.069, g2 = 2.007, g3 = 1.963), which directly reacts with benzene at −80 °C with the rate constant k2 = 0.6 M−1s−1, and with toluene with k2 > 1 M−1s−1, thus giving evidence for its key role in the selective oxygenation of aromatic substrates.",

keywords = "Aromatic oxidation, Electrophilic substitution, Hydrogen peroxide, Intermediates, Iron, Oxidation, OXIDATION, BENZENE, EPR, REACTIVITY, EPOXIDATION, HYDROGEN-PEROXIDE, SELECTIVITY, CATALYSTS, FE",

author = "Tkachenko, {Nikolay V.} and Lyakin, {Oleg Y.} and Zima, {Alexandra M.} and Talsi, {Evgenii P.} and Bryliakov, {Konstantin P.}",

note = "Publisher Copyright: {\textcopyright} 2018 Elsevier B.V.",

year = "2018",

month = sep,

day = "15",

doi = "10.1016/j.jorganchem.2018.07.016",

language = "English",

volume = "871",

pages = "130--134",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

}

RIS

TY - JOUR

T1 - Effect of different carboxylic acids on the aromatic hydroxylation with H2O2 in the presence of an iron aminopyridine complex

AU - Tkachenko, Nikolay V.

AU - Lyakin, Oleg Y.

AU - Zima, Alexandra M.

AU - Talsi, Evgenii P.

AU - Bryliakov, Konstantin P.

PY - 2018/9/15

Y1 - 2018/9/15

N2 - In this contribution, the effect of the structure of the catalytic additive – carboxylic acid – on the catalytic performance of the iron based catalyst [(PDP)Fe(OTf)2], 2 (PDP = N,N′-bis(2-pyridylmethyl)-(S,S)-2,2′-bipyrrolidine) in the selective aromatic oxidation of alkylbenzenes with H2O2 is presented. Eight (linear and branched) carboxylic acids have been tested; in the presence of 2-ethylhexanoic acid, the system [(PDP)Fe(OTf)2]/RCOOH/H2O2 has demonstrated the highest substrate conversion and the highest selectivity for oxygen incorporation into the aromatic ring (up to > 99%) at the same time. Low-temperature EPR spectroscopic study of the system [(PDP)Fe(OTf)2]/2-ethylhexanoic acid/H2O2 witness the presence of the low-spin perferryl intermediate 2aEHA with small g-factor anisotropy (g1 = 2.069, g2 = 2.007, g3 = 1.963), which directly reacts with benzene at −80 °C with the rate constant k2 = 0.6 M−1s−1, and with toluene with k2 > 1 M−1s−1, thus giving evidence for its key role in the selective oxygenation of aromatic substrates.

AB - In this contribution, the effect of the structure of the catalytic additive – carboxylic acid – on the catalytic performance of the iron based catalyst [(PDP)Fe(OTf)2], 2 (PDP = N,N′-bis(2-pyridylmethyl)-(S,S)-2,2′-bipyrrolidine) in the selective aromatic oxidation of alkylbenzenes with H2O2 is presented. Eight (linear and branched) carboxylic acids have been tested; in the presence of 2-ethylhexanoic acid, the system [(PDP)Fe(OTf)2]/RCOOH/H2O2 has demonstrated the highest substrate conversion and the highest selectivity for oxygen incorporation into the aromatic ring (up to > 99%) at the same time. Low-temperature EPR spectroscopic study of the system [(PDP)Fe(OTf)2]/2-ethylhexanoic acid/H2O2 witness the presence of the low-spin perferryl intermediate 2aEHA with small g-factor anisotropy (g1 = 2.069, g2 = 2.007, g3 = 1.963), which directly reacts with benzene at −80 °C with the rate constant k2 = 0.6 M−1s−1, and with toluene with k2 > 1 M−1s−1, thus giving evidence for its key role in the selective oxygenation of aromatic substrates.

KW - Aromatic oxidation

KW - Electrophilic substitution

KW - Hydrogen peroxide

KW - Intermediates

KW - Iron

KW - Oxidation

KW - OXIDATION

KW - BENZENE

KW - EPR

KW - REACTIVITY

KW - EPOXIDATION

KW - HYDROGEN-PEROXIDE

KW - SELECTIVITY

KW - CATALYSTS

KW - FE

UR - http://www.scopus.com/inward/record.url?scp=85049985652&partnerID=8YFLogxK

U2 - 10.1016/j.jorganchem.2018.07.016

DO - 10.1016/j.jorganchem.2018.07.016

M3 - Article

AN - SCOPUS:85049985652

VL - 871

SP - 130

EP - 134

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -

ID: 14869865