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 |
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| 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 |
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| Affiliations |
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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 OpenAlex AN
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 OpenAlex AN
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 |
| ≡ OpenAlex: | W4293659835 |
| ≡ Chemical Abstracts: | 2022:2500650 |