Highly Efficient Aromatic C−H Oxidation with H2O2 in the Presence of Iron Complexes of the PDP Family Full article
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ChemCatChem
ISSN: 1867-3880 , E-ISSN: 1867-3899 |
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| 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 | ||||||
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| Affiliations |
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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
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 |