TY - JOUR
T1 - Nitrite to nitric oxide interconversion by heme FeII complex assisted by [CuI(tmpa)]+
AU - Turias, Francesc
AU - Solà, Miquel
AU - Falivene, Laura
AU - Cavallo, Luigi
AU - Poater, Albert
N1 - KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: Federación Española de Enfermedades Raras[UNGI10-4E-801, UNGI08-4E-003]
PY - 2015/9/9
Y1 - 2015/9/9
N2 - 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
AB - 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
UR - http://hdl.handle.net/10754/594236
UR - http://link.springer.com/10.1007/s11224-015-0670-0
UR - http://www.scopus.com/inward/record.url?scp=84957429572&partnerID=8YFLogxK
U2 - 10.1007/s11224-015-0670-0
DO - 10.1007/s11224-015-0670-0
M3 - Article
SN - 1040-0400
VL - 27
SP - 409
EP - 417
JO - Structural Chemistry
JF - Structural Chemistry
IS - 1
ER -