Determining the Inherent Selectivity for Carbon Radical Hydroxylation versus Halogenation with FeIII(OH)(X) Complexes: Relevance to the Rebound Step in Non-heme Iron Halogenases.
J Am Chem Soc
; 142(16): 7259-7264, 2020 04 22.
Article
em En
| MEDLINE
| ID: mdl-32281794
ABSTRACT
The first structural models of the proposed cis-FeIII(OH)(halide) intermediate in the non-heme iron halogenases were synthesized and examined for their inherent reactivity with tertiary carbon radicals. Selective hydroxylation occurs for these cis-FeIII(OH)(X) (X = Cl, Br) complexes in a radical rebound-like process. In contrast, a cis-FeIII(Cl)2 complex reacts with carbon radicals to give halogenation. These results are discussed in terms of the inherent reactivity of the analogous rebound intermediate in both enzymes and related catalysts.
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1
Base de dados:
MEDLINE
Assunto principal:
Carbono
/
Halogenação
/
Hidroxilação
/
Ferro
Idioma:
En
Ano de publicação:
2020
Tipo de documento:
Article