Sciact
  • EN
  • RU

Effect of Brønsted Acid on the Reactivity and Selectivity of the Oxoiron(V) Intermediates in C-H and C=C Oxidation Reactions Full article

Journal Catalysts
ISSN: 2073-4344
Output data Year: 2022, Volume: 12, Number: 9, Article number : 949, Pages count : 14 DOI: 10.3390/catal12090949
Tags C-H activation; intermediate; iron; mechanism; non-heme; oxidation
Authors Zima Alexandra M. 1 , Lyakin Oleg Y. 1 , Bryliakova Anna A. 1 , Babushkin Dmitrii E. 1 , Bryliakov Konstantin P. 1 , Talsi Evgenii P. 1
Affiliations
1 Boreskov Institute of Catalysis, Pr. Lavrentieva 5, 630090 Novosibirsk, Russia

Funding (1)

1 Russian Science Foundation 22-13-00225

Abstract: The effect of HClO4 on the reactivity and selectivity of the catalyst systems 1,2/H2O2/AcOH, based on nonheme iron complexes of the PDP families, [(Me2OMePDP)FeIII(μ-OH)2FeIII(MeOMe2PDP)](OTf)4 (1) and [(NMe2PDP)FeIII(μ-OH)2FeIII(NMe2PDP](OTf)4 (2), toward oxidation of benzylideneacetone (bna), adamantane (ada), and (3aR)-(+)-sclareolide (S) has been studied. Adding HClO4 (2–10 equiv. vs. Fe) has been found to result in the simultaneous improvement of the observed catalytic efficiency (i.e., product yields) and the oxidation regio- or enantioselectivity. At the same time, HClO4 causes a threefold increase of the second-order rate constant for the reaction of the key oxygen-transferring intermediate [(Me2OMePDP)FeV=O(OAc)]2+ (1a), with cyclohexane at −70 °C. The effect of strong Brønsted acid on the catalytic reactivity is discussed in terms of the reversible protonation of the Fe=O moiety of the parent perferryl intermediates. © 2022 by the authors.
Cite: Zima A.M. , Lyakin O.Y. , Bryliakova A.A. , Babushkin D.E. , Bryliakov K.P. , Talsi E.P.
Effect of Brønsted Acid on the Reactivity and Selectivity of the Oxoiron(V) Intermediates in C-H and C=C Oxidation Reactions
Catalysts. 2022. V.12. N9. 949 :1-14. DOI: 10.3390/catal12090949 WOS Scopus РИНЦ AN OpenAlex
Dates:
Submitted: Aug 9, 202
Accepted: Aug 22, 2022
Published online: Aug 26, 2022
Published print: Sep 1, 2022
Identifiers:
Web of science: WOS:000857672500001
Scopus: 2-s2.0-85138615780
Elibrary: 52650505
Chemical Abstracts: 2022:2500650
OpenAlex: W4293659835
Citing:
DB Citing
Scopus 5
Web of science 5
Elibrary 5
OpenAlex 5
Altmetrics: