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Highly Efficient Aromatic C−H Oxidation with H2O2 in the Presence of Iron Complexes of the PDP Family Full article

Journal ChemCatChem
ISSN: 1867-3880 , E-ISSN: 1867-3899
Output data Year: 2018, Volume: 10, Number: 18, Pages: 4052-4057 Pages count : 6 DOI: 10.1002/cctc.201800832
Tags Aromatic substitution; hydrogen peroxide; intermediates; iron; oxidation
Authors Tkachenko Nikolay V. 1,2 , Ottenbacher Roman V. 1,2 , Lyakin Oleg Y. 1,2 , Zima Alexandra M. 1,2 , Samsonenko Denis G. 2,3 , Talsi Evgenii P. 1,2 , Bryliakov Konstantin P. 1,2
Affiliations
1 Boreskov Institute of Catalysis Pr. Lavrentieva 5 Novosibirsk 630090 Russia
2 Novosibirsk State University Pirogova 2 Novosibirsk 630090 Russia
3 Nikolaev Institute of Inorganic Chemistry Pr. Lavrentieva 3 Novosibirsk 630090 Russia

Funding (2)

1 Russian Science Foundation 17-13-01117
2 Russian Foundation for Basic Research 18-33-00462

Abstract: The catalytic activity of a series of iron complexes of the PDP family (PDP=N,N′‐bis(2‐pyridylmethyl)‐2,2′‐bipyrrolidine) in the oxidation of aromatic substrates with H2O2 has been studied. In the presence of acetic acid, these complexes efficiently catalyze the oxidation of benzene and alkylbenzenes with high selectivity for oxygen incorporation into the aromatic ring (up to 93 %), performing up to 84 catalytic turnovers. The parent complex, [(PDP)(OTf)2], has demonstrated the highest catalytic efficiency and aromatic oxidation selectivity. The yield of products of oxidation of different substrates increases in line with increasing number of electron‐donating alkyl groups of the substrates: halogenbenzenes<benzene<monoalkylbenzenes<dialkylbenzenes, which, together with the results of competitive oxidation experiments and the observation of inverse primary kH/kD (0.90–0.92), agrees with the SEAr oxidation mechanism. Low‐temperature EPR studies have witnessed the presence of low‐spin (g1=2.071, g2=2.008, g3=1.960) perferryl intermediates, demonstrating direct reactivity toward benzene. The oxidation of m‐xylene in the presence of H218O has shown the same probability of 18O incorporation into the aromatic ring and the aliphatic moieties, which is indicative that both the aromatic and aliphatic oxidations are conducted by the same active species.
Cite: Tkachenko N.V. , Ottenbacher R.V. , Lyakin O.Y. , Zima A.M. , Samsonenko D.G. , Talsi E.P. , Bryliakov K.P.
Highly Efficient Aromatic C−H Oxidation with H2O2 in the Presence of Iron Complexes of the PDP Family
ChemCatChem. 2018. V.10. N18. P.4052-4057. DOI: 10.1002/cctc.201800832 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
Submitted: May 21, 2018
Published online: Jun 19, 2018
Published print: Sep 20, 2018
Identifiers:
Web of science: WOS:000445176700020
Scopus: 2-s2.0-85049933145
Elibrary: 35754409
Chemical Abstracts: 2018:1346784
Chemical Abstracts (print): 169:326600
OpenAlex: W2808773946
Citing:
DB Citing
Web of science 26
Scopus 27
Elibrary 26
OpenAlex 26
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