Highly Efficient Aromatic C−H Oxidation with H2O2 in the Presence of Iron Complexes of the PDP Family | Sciact - CRIS-система Института катализа

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

Журнал

ChemCatChem
ISSN: 1867-3880 , E-ISSN: 1867-3899

Вых. Данные

Год: 2018, Том: 10, Номер: 18, Страницы: 4052-4057 Страниц : 6 DOI: 10.1002/cctc.201800832

Ключевые слова

Aromatic substitution; hydrogen peroxide; intermediates; iron; oxidation

Авторы

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

Организации

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

Информация о финансировании (2)

1	Российский научный фонд	17-13-01117
2	Российский фонд фундаментальных исследований	18-33-00462

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.

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 CAPlusCA OpenAlex

Поступила в редакцию:	21 мая 2018 г.
Опубликована online:	19 июн. 2018 г.
Опубликована в печати:	20 сент. 2018 г.

Web of science:	WOS:000445176700020
Scopus:	2-s2.0-85049933145
РИНЦ:	35754409
Chemical Abstracts:	2018:1346784
Chemical Abstracts (print):	169:326600
OpenAlex:	W2808773946

БД	Цитирований
Web of science	24
Scopus	25
РИНЦ	25
OpenAlex	24