Repozytorium

Dioxygen insertion into iron(III)-carbon bonds : NMR studies of the formation and reactivity of alkylperoxo complexes of iron(III) porphyrins.

Autorzy

R. D. Arasasingham

Alan L. Balch

C. R. Cornman

Lechosław Latos-Grażyński

Rok wydania

1989

Czasopismo

Journal of the American Chemical Society

Numer woluminu

111

Strony

4357-4363

DOI

10.1021/ja00194a031

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

The behavior of PFemCHR2 (P is a porphyrin dianion) in solution especially in the presence of dioxygen has been examined by and 2H NMR measurements. Evidence for the photolytic Fe-C bond homolysis with the formation of PFe11 is presented. Addition of dioxygen to PFeCH2R produces two unstable intermediates, PFem02CH2R and PFemOH, whichmay be directly observed at low temperatures. These form and decompose through the following reactions: PFemCH2R +
02 -» PFeln02CHR2; PFenl02CHR2 — PFemOH + G=CR2; 2PFeUIOH — PFe,nOFelnP + H20. The formation of the product aldehyde or ketone has been established for methyl, ethyl, isopropyl, «-propyl, and benzyl ligands axially coordinating iron. The dioxygen insertion is retarded by the coordination of TV-methylimidazole to the sixth iron coordination site or by employing a sterically encumbered porphyrin. PFenlOH catalyzes the decomposition of ethyl hydroperoxide to give acetaldehydeas the major organic product.

Adres publiczny

https://doi.org/10.1021/ja00194a031

Strona internetowa wydawcy

https://www.acs.org/content/acs/en.html

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Wołowiec Stanisław, Latos-Grażyński Lechosław, Zakrzewski J.