Direct Evaluation of the Reactivity of Nonheme Iron(V)–Oxo Intermediates toward Arenes Full article
| Journal |
ACS Catalysis
ISSN: 2155-5435 |
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| Output data | Year: 2018, Volume: 8, Pages: 5255-5260 Pages count : 6 DOI: 10.1021/acscatal.8b00661 | ||||
| Tags | aromatic C−H oxidation; enzyme models; EPR; iron; mechanism | ||||
| Authors |
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| Affiliations |
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Funding (1)
| 1 | Russian Science Foundation | 17-13-01117 |
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%).
Cite:
Lyakin O.Y.
, Zima A.M.
, Tkachenko N.V.
, Bryliakov K.P.
, Talsi E.P.
Direct Evaluation of the Reactivity of Nonheme Iron(V)–Oxo Intermediates toward Arenes
ACS Catalysis. 2018. V.8. P.5255-5260. DOI: 10.1021/acscatal.8b00661 WOS Scopus РИНЦ ANCAN OpenAlex
Direct Evaluation of the Reactivity of Nonheme Iron(V)–Oxo Intermediates toward Arenes
ACS Catalysis. 2018. V.8. P.5255-5260. DOI: 10.1021/acscatal.8b00661 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
| Submitted: | Feb 16, 2018 |
| Published online: | May 1, 2018 |
| Published print: | Jun 1, 2018 |
Identifiers:
| Web of science: | WOS:000434369600052 |
| Scopus: | 2-s2.0-85046545514 |
| Elibrary: | 38607752 |
| Chemical Abstracts: | 2018:878336 |
| Chemical Abstracts (print): | 170:534480 |
| OpenAlex: | W2801856951 |