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
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 in...
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todo:paper_00201669_v40_n17_p4127_Lebrero2023-10-03T14:16:50Z 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 Lebrero, M.C.G. Scherlis, D.A. Estiú, G.L. Olabe, J.A. Estrin, D.A. 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 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. Fil:Olabe, J.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Estrin, D.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00201669_v40_n17_p4127_Lebrero |
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Universidad de Buenos Aires |
| institution_str |
I-28 |
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R-134 |
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
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 |
| spellingShingle |
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 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 |
| topic_facet |
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 |
| description |
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. |
| format |
JOUR |
| author |
Lebrero, M.C.G. Scherlis, D.A. Estiú, G.L. Olabe, J.A. Estrin, D.A. |
| author_facet |
Lebrero, M.C.G. Scherlis, D.A. Estiú, G.L. Olabe, J.A. Estrin, D.A. |
| author_sort |
Lebrero, M.C.G. |
| title |
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 |
| title_short |
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 |
| title_full |
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 |
| title_fullStr |
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 |
| title_full_unstemmed |
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 |
| title_sort |
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 |
| url |
http://hdl.handle.net/20.500.12110/paper_00201669_v40_n17_p4127_Lebrero |
| work_keys_str_mv |
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| _version_ |
1807322866543230976 |