Iron(IV) or iron(V)? Heterolytic or free radical? Oxidation pathways of a TAML activator in acetonitrile at −40 °C

Autor:	Abigail E. Burton, Matthew R. Mills, Alexander D. Ryabov, Dylan I. Mori, Terrence J. Collins
Rok vydání:	2015
Předmět:	Chemistry Dimer Kinetics Benzoyl peroxide Photochemistry Heterolysis Medicinal chemistry Free Radical Process chemistry.chemical_compound Activator (phosphor) Materials Chemistry medicine Moiety Physical and Theoretical Chemistry Acetonitrile medicine.drug
Zdroj:	Journal of Coordination Chemistry. 68:3046-3057
ISSN:	1029-0389 0095-8972
Popis:	The oxidation of TAML complex (1) by various oxidants is explored in MeCN with 0.2% water at −40 °C, where the iron(V)oxo complex is stable enough for reliable spectral identification. The iron(V)oxo state is achieved using NaClO even faster than in the case of previously explored m-chloroperoxybenzoic acid. In contrast, H2O2 and organic peroxides (benzoyl peroxide, tert-butylperoxide, and tert-butylhydroperoxide) all convert 1 into the corresponding diiron(IV)-μ-oxo dimer (2) under the same conditions. The latter does not form when (NH4)2[Ce(NO3)6] is employed and the FeIV product obtained does not seem to contain an oxo moiety. In contrast to all other oxidants, the conversion of 1 by tBuOOH into 2 is characterized by non-conventional kinetics, and therefore this reaction was explored in some detail. The evidence is presented that this light-, O2-, TEMPO-, and base-dependent reaction is a free radical process under the conditions used.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::52e21fc6fc6e68bc42230f5fddb75a3b https://doi.org/10.1080/00958972.2015.1073270 Zobrazit plný text záznamu Plný text ve formátu PDF Plný text ve formátu HTML
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