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

The effect of β-substituents (-NO2, -Br, -OCH3) in the reactivity of Fe(II) and Fe(III) porphyrins is studied by means of density funcional 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...

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Autores principales:	Bikiel, Damian Ezequiel, Bari, Sara Elizabeth, Doctorovich, Fabio Ariel, Estrin, Dario Ariel
Publicado:	2008
Materias:	Binding energy CO NO O2 Substituted porphyrins carbon monoxide ferric ion ferrous ion ligand metalloporphyrin nitric oxide oxygen porphyrin derivative article complex formation density functional theory energy geometry ligand binding molecular interaction oxidation reduction reaction Computer Simulation Ferrous Compounds Heme Metalloporphyrins Molecular Structure Thermodynamics
Acceso en línea:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01620134_v102_n1_p70_Bikiel http://hdl.handle.net/20.500.12110/paper_01620134_v102_n1_p70_Bikiel
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	paper:paper_01620134_v102_n1_p70_Bikiel
record_format	dspace
spelling	paper:paper_01620134_v102_n1_p70_Bikiel2023-06-08T15:13:33Z DFT study on the reactivity of iron porphyrins tuned by ring substitution Bikiel, Damian Ezequiel Bari, Sara Elizabeth Doctorovich, Fabio Ariel Estrin, Dario Ariel Binding energy CO NO O2 Substituted porphyrins carbon monoxide ferric ion ferrous ion ligand metalloporphyrin nitric oxide oxygen porphyrin derivative article complex formation density functional theory energy geometry ligand binding molecular interaction oxidation reduction reaction Computer Simulation Ferrous Compounds Heme Metalloporphyrins Molecular Structure Thermodynamics The effect of β-substituents (-NO2, -Br, -OCH3) in the reactivity of Fe(II) and Fe(III) porphyrins is studied by means of density funcional 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. © 2007 Elsevier Inc. All rights reserved. Fil:Bikiel, D.E. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Bari, S.E. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Doctorovich, F. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Estrin, D.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2008 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01620134_v102_n1_p70_Bikiel http://hdl.handle.net/20.500.12110/paper_01620134_v102_n1_p70_Bikiel
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	Binding energy CO NO O2 Substituted porphyrins carbon monoxide ferric ion ferrous ion ligand metalloporphyrin nitric oxide oxygen porphyrin derivative article complex formation density functional theory energy geometry ligand binding molecular interaction oxidation reduction reaction Computer Simulation Ferrous Compounds Heme Metalloporphyrins Molecular Structure Thermodynamics
spellingShingle	Binding energy CO NO O2 Substituted porphyrins carbon monoxide ferric ion ferrous ion ligand metalloporphyrin nitric oxide oxygen porphyrin derivative article complex formation density functional theory energy geometry ligand binding molecular interaction oxidation reduction reaction Computer Simulation Ferrous Compounds Heme Metalloporphyrins Molecular Structure Thermodynamics Bikiel, Damian Ezequiel Bari, Sara Elizabeth Doctorovich, Fabio Ariel Estrin, Dario Ariel DFT study on the reactivity of iron porphyrins tuned by ring substitution
topic_facet	Binding energy CO NO O2 Substituted porphyrins carbon monoxide ferric ion ferrous ion ligand metalloporphyrin nitric oxide oxygen porphyrin derivative article complex formation density functional theory energy geometry ligand binding molecular interaction oxidation reduction reaction Computer Simulation Ferrous Compounds Heme Metalloporphyrins Molecular Structure Thermodynamics
description	The effect of β-substituents (-NO2, -Br, -OCH3) in the reactivity of Fe(II) and Fe(III) porphyrins is studied by means of density funcional 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. © 2007 Elsevier Inc. All rights reserved.
author	Bikiel, Damian Ezequiel Bari, Sara Elizabeth Doctorovich, Fabio Ariel Estrin, Dario Ariel
author_facet	Bikiel, Damian Ezequiel Bari, Sara Elizabeth Doctorovich, Fabio Ariel Estrin, Dario Ariel
author_sort	Bikiel, Damian Ezequiel
title	DFT study on the reactivity of iron porphyrins tuned by ring substitution
title_short	DFT study on the reactivity of iron porphyrins tuned by ring substitution
title_full	DFT study on the reactivity of iron porphyrins tuned by ring substitution
title_fullStr	DFT study on the reactivity of iron porphyrins tuned by ring substitution
title_full_unstemmed	DFT study on the reactivity of iron porphyrins tuned by ring substitution
title_sort	dft study on the reactivity of iron porphyrins tuned by ring substitution
publishDate	2008
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01620134_v102_n1_p70_Bikiel http://hdl.handle.net/20.500.12110/paper_01620134_v102_n1_p70_Bikiel
work_keys_str_mv	AT bikieldamianezequiel dftstudyonthereactivityofironporphyrinstunedbyringsubstitution AT barisaraelizabeth dftstudyonthereactivityofironporphyrinstunedbyringsubstitution AT doctorovichfabioariel dftstudyonthereactivityofironporphyrinstunedbyringsubstitution AT estrindarioariel dftstudyonthereactivityofironporphyrinstunedbyringsubstitution
_version_	1768541982009851904

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

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