Nitrite to nitric oxide interconversion by heme FeII complex assisted by [CuI(tmpa)]+

The present computational study complements the recent experimental efforts by Karlin and coworkers to describe the interconversion of nitrite to nitric oxide by means of an iron porphyrin complex together with a Cu chemical system, i.e., the iron(II) complex (F8TPP)FeII [F8TPP = tetrakis(2,6-difluo...

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Detalles Bibliográficos
Autores: Turias, Francesc, Solà i Puig, Miquel, Falivene, Laura, Cavallo, Luigi, Poater i Teixidor, Jordi
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2016
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/12374
Acceso en línea:http://hdl.handle.net/10256/12374
Access Level:acceso embargado
Palabra clave:Catalitzadors de coure
Copper catalysts
Citocrom c
Cytochrome c
Hem oxigenasa
Heme oxygenase
Catalitzadors de ferro
Iron catalysts
Òxid nítric
Nitric oxide
Nitrurs
Nitrides
Descripción
Sumario:The present computational study complements the recent experimental efforts by Karlin and coworkers to describe the interconversion of nitrite to nitric oxide by means of an iron porphyrin complex together with a Cu chemical system, i.e., the iron(II) complex (F8TPP)FeII [F8TPP = tetrakis(2,6-difluorophenyl)porphyrinate(2-)] and a preformed copper(II)-nitrito complex [(tmpa)CuII(NO2)][B(C6F5)4] [tmpa = tris(2-pyridylmethyl)amine], being the latter an oxidized species of [(tmpa)CuI(MeCN)]+. By DFT calculations, we unravel how the reduction of nitrite to nitric oxide takes place through a μ-oxo heme-FeIII-O-CuII complex, following a mimetic path as in the cytochrome c oxidase. Mayer bond order (MBO) and energy decomposition analyses are used to analyze the bonding strength of such nitro derivatives to either copper or iron