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

Handle URI:
http://hdl.handle.net/10754/594236
Title:
Nitrite to nitric oxide interconversion by heme FeII complex assisted by [CuI(tmpa)]+
Authors:
Turias, Francesc; Solà, Miquel; Falivene, Laura ( 0000-0003-1509-6191 ) ; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Poater, Albert ( 0000-0002-8997-2599 )
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. © 2015 Springer Science+Business Media New York
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Turias F, Solà M, Falivene L, Cavallo L, Poater A (2015) Nitrite to nitric oxide interconversion by heme FeII complex assisted by [CuI(tmpa)]+. Struct Chem. Available: http://dx.doi.org/10.1007/s11224-015-0670-0.
Publisher:
Springer Science + Business Media
Journal:
Structural Chemistry
Issue Date:
9-Sep-2015
DOI:
10.1007/s11224-015-0670-0
Type:
Article
ISSN:
1040-0400; 1572-9001
Sponsors:
Federación Española de Enfermedades Raras[UNGI10-4E-801, UNGI08-4E-003]; Ministerio de Economía y Competitividad[CTQ2014-54306-P, CTQ2014-59832-JIN]; Generalitat de Catalunya[ICREA Academia 2014, 2014SGR931]; European Commission[CIG09-GA-2011-293900]
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorTurias, Francescen
dc.contributor.authorSolà, Miquelen
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorPoater, Alberten
dc.date.accessioned2016-01-19T14:44:03Zen
dc.date.available2016-01-19T14:44:03Zen
dc.date.issued2015-09-09en
dc.identifier.citationTurias F, Solà M, Falivene L, Cavallo L, Poater A (2015) Nitrite to nitric oxide interconversion by heme FeII complex assisted by [CuI(tmpa)]+. Struct Chem. Available: http://dx.doi.org/10.1007/s11224-015-0670-0.en
dc.identifier.issn1040-0400en
dc.identifier.issn1572-9001en
dc.identifier.doi10.1007/s11224-015-0670-0en
dc.identifier.urihttp://hdl.handle.net/10754/594236en
dc.description.abstractThe 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. © 2015 Springer Science+Business Media New Yorken
dc.description.sponsorshipFederación Española de Enfermedades Raras[UNGI10-4E-801, UNGI08-4E-003]en
dc.description.sponsorshipMinisterio de Economía y Competitividad[CTQ2014-54306-P, CTQ2014-59832-JIN]en
dc.description.sponsorshipGeneralitat de Catalunya[ICREA Academia 2014, 2014SGR931]en
dc.description.sponsorshipEuropean Commission[CIG09-GA-2011-293900]en
dc.publisherSpringer Science + Business Mediaen
dc.subjectCopper catalysten
dc.subjectCytochrome c oxidaseen
dc.subjectHemeen
dc.subjectIron catalysten
dc.subjectNitric oxideen
dc.subjectNitriteen
dc.titleNitrite to nitric oxide interconversion by heme FeII complex assisted by [CuI(tmpa)]+en
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalStructural Chemistryen
dc.contributor.institutionInstitut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus Montilivi, Girona, Catalonia, Spainen
kaust.authorTurias, Francescen
kaust.authorFalivene, Lauraen
kaust.authorCavallo, Luigien
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