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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-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

A. P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN and European Commission for a Career Integration Grant (CIG09-GA-2011-293900). M. S. thanks the Generalitat de Catalunya for project 2014SGR931 and ICREA Academia 2014 prize, and MINECO of Spain through project CTQ2014-54306-P. A. P. and M. S. thank EU for the FEDER fund UNGI10-4E-801

© Structural Chemistry, 2016, vol. 27, núm. 1, p. 409-417

Springer Verlag

Author: Turias, Francesc
Solà i Puig, Miquel
Falivene, Laura
Cavallo, Luigi
Poater i Teixidor, Jordi
Date: 2016
Abstract: 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
A. P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN and European Commission for a Career Integration Grant (CIG09-GA-2011-293900). M. S. thanks the Generalitat de Catalunya for project 2014SGR931 and ICREA Academia 2014 prize, and MINECO of Spain through project CTQ2014-54306-P. A. P. and M. S. thank EU for the FEDER fund UNGI10-4E-801
Format: application/pdf
ISSN: 1040-0400 (versió paper)
1572-9001 (versió electrònica)
Document access: http://hdl.handle.net/10256/12374
Language: eng
Publisher: Springer Verlag
Collection: MINECO/PE 2015-2018/CTQ2014-59832-JIN
AGAUR/2014-2016/2014 SGR-931
MINECO/PE 2015-2017/CTQ2014-54306-P
Reproducció digital del document publicat a: http://dx.doi.org/10.1007/s11224-015-0670-0
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/293900
Is part of: © Structural Chemistry, 2016, vol. 27, núm. 1, p. 409-417
Rights: Tots els drets reservats
Subject: Catalitzadors de coure
Copper catalysts
Citocrom c
Cytochrome c
Hem oxigenasa
Heme oxygenase
Catalitzadors de ferro
Iron catalysts
Òxid nítric
Nitric oxide
Nitrurs
Nitrides
Title: Nitrite to nitric oxide interconversion by heme FeII complex assisted by [CuI(tmpa)]+
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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