Sciact
  • EN
  • RU

Low‐Spin and High‐Spin Perferryl Intermediates in Non‐Heme Iron Catalyzed Oxidations of Aliphatic C–H Groups Full article

Journal Chemistry - A European Journal
ISSN: 0947-6539 , E-ISSN: 1521-3765
Output data Year: 2021, Volume: 27, Number: 28, Pages: 7781-7788 Pages count : 8 DOI: 10.1002/chem.202004395
Tags biomimetic chemistry; iron; intermediate; oxidation; selectivity
Authors Zima Alexandra M. 1 , Lyakin Oleg Y. 1 , Bryliakov Konstantin Petrovich 1 , Talsi Evgenii P. 1
Affiliations
1 Boreskov Institute of Catalysis

Funding (1)

1 Russian Science Foundation 17-13-01117

Abstract: The selectivity patterns of iron catalysts of the Fe(PDP) family in aliphatic C–H oxidation with H 2 O 2 have been studied (PDP = N , N ′‐bis(pyridine‐2‐ylmethyl)‐2,2′‐bipyrrolidine). Cyclohexane, adamantane, 1‐bromo‐3,7‐dimethyloctane, 3,7‐dimethyloctyl acetate, (–)‐acetoxy‐ p ‐menthane, and cis ‐1,2‐dimethylcyclohexane were used as substrates. The studied catalyst systems generate low‐spin ( S = 1/2) oxoiron(V) intermediates or high‐spin ( S = 3/2) oxoiron(V) intermediates, depending on the electron‐donating ability of remote substituents at the pyridine rings. The low‐spin perferryl intermediates demonstrate lower stability and higher reactivity toward aliphatic C–H groups of cyclohexane than their high‐spin congeners, according to the measured self‐decay and second‐order rate constants k 1 and k 2 . Unexpectedly, there appears to be no uniform correlation between the spin state of the oxoiron(V) intermediates, and the chemo‐ and regioselectivity of the corresponding catalyst systems in the oxidation of the considered substrates. This contrasts with the asymmetric epoxidations by the same catalyst systems, in which case the epoxidation enantioselectivity increases when passing from the systems featuring the more reactive low‐spin perferryl intermediates to those with their less reactive high‐spin congeners.
Cite: Zima A.M. , Lyakin O.Y. , Bryliakov K.P. , Talsi E.P.
Low‐Spin and High‐Spin Perferryl Intermediates in Non‐Heme Iron Catalyzed Oxidations of Aliphatic C–H Groups
Chemistry - A European Journal. 2021. V.27. N28. P.7781-7788. DOI: 10.1002/chem.202004395 WOS Scopus РИНЦ ANCAN PMID OpenAlex
Dates:
Submitted: Sep 29, 2020
Accepted: Mar 29, 2021
Published online: Mar 29, 2021
Published print: May 17, 2021
Identifiers:
Web of science: WOS:000645494000001
Scopus: 2-s2.0-85105170010
Elibrary: 46035648
Chemical Abstracts: 2021:1009054
Chemical Abstracts (print): 177:60156
PMID: 33780054
OpenAlex: W3148336394
Citing:
DB Citing
Web of science 8
Scopus 8
Elibrary 9
OpenAlex 8
Altmetrics: