DFT study on the reactivity of iron porphyrins tuned by ring substitution.

Bikiel, Damián E; Bari, Sara E; Doctorovich, Fabio; Estrin, Darío A

Bikiel, Damián E; Bari, Sara E; Doctorovich, Fabio; Estrin, Darío A.

Afiliação

Bikiel DE; Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Buenos Aires, Argentina.

J Inorg Biochem ; 102(1): 70-6, 2008 Jan.

Article em En | MEDLINE | ID: mdl-17723244

RESUMO

The effect of beta-substituents (-NO2, -Br, -OCH3) in the reactivity of Fe(II) and Fe(III) porphyrins is studied by means of density functional theory (DFT) calculations. The binding of nitric oxide, carbon monoxide and dioxygen (NO, CO, O2) was explored due to the relevance of their interactions in the chemistry of heme proteins and in biomimetic catalysis. The binding capability (BC) of the porphyrins was found to be strongly modulated both by the donor and attractor substituents used in the work. Unexpectedly, we found that the BC of Fe(II) porphyrins is mainly decreased for the diatomic ligands, when both donor or withdrawing substituents were considered. This effect was particularly significant when the ligand was oxygen. The correlation of Fe-X and X-O (X=N, C, O) bond distances is explained in terms of backdonation effects.

Assuntos

Compostos Ferrosos/química; Metaloporfirinas/química; Simulação por Computador; Heme/química; Estrutura Molecular; Termodinâmica

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Coleções: 01-internacional Base de dados: MEDLINE Assunto principal: Compostos Ferrosos / Metaloporfirinas Idioma: En Revista: J Inorg Biochem Ano de publicação: 2008 Tipo de documento: Article País de afiliação: Argentina País de publicação: Estados Unidos

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