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Abstract:

Reaction pathways for the one- and two-electron reductions of [Fe(CN)5NO]2- have been investigated by means of a density functional theory (DFT) approach combined with the polarized continuum model (PCM) of solvation. In addition, UV-vis spectroscopic data were obtained using ZINDO/S calculations including a point-charge model simulation of solvent effects. DFT methodologies have been used to assess the thermodynamical feasibility of protonation and cyanide-release processes for the reduced species. We conclude that [Fe(CN)5NO]3- is a stable species in aqueous solution but may release cyanide yielding [Fe(CN)4NO]2-, consistent with experimental results. On the other hand, the [Fe(CN)5NO]4- complex turns out to be unstable in solution, yielding the product of cyanide release, [Fe(CN)4NO]3-, and/or the protonated HNO complex. All the structural and spectroscopic (IR, UV-vis) predictions for the [Fe(CN)5HNO]3- ion are consistent with the scarce but significant experimental evidence of its presence as an intermediate in nitrogen redox interconversion chemistry. Our computed data support an FeII(LS) + NO+ assignment for [Fe(CN)5NO]2-, an FeII(LS) + NO assignment for the one-electron reduction product, but an FeI(LS) + NO+ for the one-electron product after dissociation of an axial cianide, and an FeII + singlet NO- for the two-electron reduction species.

Registro:

Documento: Artículo
Título:Theoretical investigation on the electronic structure of pentacyano(L)ferrate(II) complexes with NO+, NO, and NO- ligands. Redox interconversion, protonation, and cyanide-releasing reactions
Autor:Lebrero, M.C.G.; Scherlis, D.A.; Estiú, G.L.; Olabe, J.A.; Estrin, D.A.
Filiación:Dept.de Química Inorgánica, Analítica y Química Física, Inquimae, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 2, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina
Cequinor, Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC 962, La Plata, Argentina
Palabras clave:cyanide; iron derivative; ligand; nitric oxide; nitrogen; pentacyanoferrate derivative; unclassified drug; aqueous solution; article; calculation; chemical structure; complex formation; electron; model; oxidation reduction reaction; prediction; proton transport; reduction; simulation; solvation; structure analysis; theory; thermodynamics; ultraviolet spectroscopy
Año:2001
Volumen:40
Número:17
Página de inicio:4127
Página de fin:4133
DOI: http://dx.doi.org/10.1021/ic010140p
Título revista:Inorganic Chemistry
Título revista abreviado:Inorg. Chem.
ISSN:00201669
CODEN:INOCA
CAS:cyanide, 57-12-5; nitric oxide, 10102-43-9; nitrogen, 7727-37-9
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v40_n17_p4127_Lebrero

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Citas:

---------- APA ----------
Lebrero, M.C.G., Scherlis, D.A., Estiú, G.L., Olabe, J.A. & Estrin, D.A. (2001) . Theoretical investigation on the electronic structure of pentacyano(L)ferrate(II) complexes with NO+, NO, and NO- ligands. Redox interconversion, protonation, and cyanide-releasing reactions. Inorganic Chemistry, 40(17), 4127-4133.
http://dx.doi.org/10.1021/ic010140p
---------- CHICAGO ----------
Lebrero, M.C.G., Scherlis, D.A., Estiú, G.L., Olabe, J.A., Estrin, D.A. "Theoretical investigation on the electronic structure of pentacyano(L)ferrate(II) complexes with NO+, NO, and NO- ligands. Redox interconversion, protonation, and cyanide-releasing reactions" . Inorganic Chemistry 40, no. 17 (2001) : 4127-4133.
http://dx.doi.org/10.1021/ic010140p
---------- MLA ----------
Lebrero, M.C.G., Scherlis, D.A., Estiú, G.L., Olabe, J.A., Estrin, D.A. "Theoretical investigation on the electronic structure of pentacyano(L)ferrate(II) complexes with NO+, NO, and NO- ligands. Redox interconversion, protonation, and cyanide-releasing reactions" . Inorganic Chemistry, vol. 40, no. 17, 2001, pp. 4127-4133.
http://dx.doi.org/10.1021/ic010140p
---------- VANCOUVER ----------
Lebrero, M.C.G., Scherlis, D.A., Estiú, G.L., Olabe, J.A., Estrin, D.A. Theoretical investigation on the electronic structure of pentacyano(L)ferrate(II) complexes with NO+, NO, and NO- ligands. Redox interconversion, protonation, and cyanide-releasing reactions. Inorg. Chem. 2001;40(17):4127-4133.
http://dx.doi.org/10.1021/ic010140p