Reactivity of reduced nitroprusside, [Fe(CN)5NO .]3-, toward oxygen

In the reaction of [Fe(CN)5NO•]3- with O2 (4:1 stoichiometry), the nitroprusside ion [Fe(CN)5NO]2- (NP) was quantitatively produced. The rate law was -1/4d[Fe(CN)5NO•3-]/dt = k2[Fe(CN)5NO•3-][O2], with k2 = (3.5 ± 0.2) × 105 M-1 s-1 at 25.0 °C. The rate was insensitive to pH (range 9-11) and ionic s...

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Publicado:	2007
Materias:	nitroprusside sodium oxygen article autooxidation chemical reaction chemical reaction kinetics covalent bond reaction analysis reduction Free Radicals Nitroprusside Oxidation-Reduction Oxygen
Acceso en línea:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00027863_v129_n2_p278_Videla http://hdl.handle.net/20.500.12110/paper_00027863_v129_n2_p278_Videla
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	paper:paper_00027863_v129_n2_p278_Videla
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spelling	paper:paper_00027863_v129_n2_p278_Videla2023-06-08T14:22:42Z Reactivity of reduced nitroprusside, [Fe(CN)5NO .]3-, toward oxygen nitroprusside sodium oxygen article autooxidation chemical reaction chemical reaction kinetics covalent bond reaction analysis reduction Free Radicals Nitroprusside Oxidation-Reduction Oxygen In the reaction of [Fe(CN)5NO•]3- with O2 (4:1 stoichiometry), the nitroprusside ion [Fe(CN)5NO]2- (NP) was quantitatively produced. The rate law was -1/4d[Fe(CN)5NO•3-]/dt = k2[Fe(CN)5NO•3-][O2], with k2 = (3.5 ± 0.2) × 105 M-1 s-1 at 25.0 °C. The rate was insensitive to pH (range 9-11) and ionic strength (I = 0.1-1 M). Excess cyanide was used for minimizing the production of [Fe(CN)4NO]2-, which appeared to be much less reactive. Addition of O2 to the NO• group is proposed to generate peroxynitrite bound to Fe(III), which reacts rapidly with [Fe(CN)5NO•]3- to yield [Fe(CN)5NO2•]3-. Reaction between the latter radical ions leads to the final product, NP. Comparison with the autoxidation rates for other NO• complexes reveals that the rate constants decrease with an increase in ENO+/NO, the redox potentials of the bound NO+/NO• couples. Six-coordination appears to be necessary for attaining reasonable electrophilic rates for the NO• ligand, as with other heme and non-heme complexes. Copyright © 2006 American Chemical Society. 2007 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00027863_v129_n2_p278_Videla http://hdl.handle.net/20.500.12110/paper_00027863_v129_n2_p278_Videla
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	nitroprusside sodium oxygen article autooxidation chemical reaction chemical reaction kinetics covalent bond reaction analysis reduction Free Radicals Nitroprusside Oxidation-Reduction Oxygen
spellingShingle	nitroprusside sodium oxygen article autooxidation chemical reaction chemical reaction kinetics covalent bond reaction analysis reduction Free Radicals Nitroprusside Oxidation-Reduction Oxygen Reactivity of reduced nitroprusside, [Fe(CN)5NO .]3-, toward oxygen
topic_facet	nitroprusside sodium oxygen article autooxidation chemical reaction chemical reaction kinetics covalent bond reaction analysis reduction Free Radicals Nitroprusside Oxidation-Reduction Oxygen
description	In the reaction of [Fe(CN)5NO•]3- with O2 (4:1 stoichiometry), the nitroprusside ion [Fe(CN)5NO]2- (NP) was quantitatively produced. The rate law was -1/4d[Fe(CN)5NO•3-]/dt = k2[Fe(CN)5NO•3-][O2], with k2 = (3.5 ± 0.2) × 105 M-1 s-1 at 25.0 °C. The rate was insensitive to pH (range 9-11) and ionic strength (I = 0.1-1 M). Excess cyanide was used for minimizing the production of [Fe(CN)4NO]2-, which appeared to be much less reactive. Addition of O2 to the NO• group is proposed to generate peroxynitrite bound to Fe(III), which reacts rapidly with [Fe(CN)5NO•]3- to yield [Fe(CN)5NO2•]3-. Reaction between the latter radical ions leads to the final product, NP. Comparison with the autoxidation rates for other NO• complexes reveals that the rate constants decrease with an increase in ENO+/NO, the redox potentials of the bound NO+/NO• couples. Six-coordination appears to be necessary for attaining reasonable electrophilic rates for the NO• ligand, as with other heme and non-heme complexes. Copyright © 2006 American Chemical Society.
title	Reactivity of reduced nitroprusside, [Fe(CN)5NO .]3-, toward oxygen
title_short	Reactivity of reduced nitroprusside, [Fe(CN)5NO .]3-, toward oxygen
title_full	Reactivity of reduced nitroprusside, [Fe(CN)5NO .]3-, toward oxygen
title_fullStr	Reactivity of reduced nitroprusside, [Fe(CN)5NO .]3-, toward oxygen
title_full_unstemmed	Reactivity of reduced nitroprusside, [Fe(CN)5NO .]3-, toward oxygen
title_sort	reactivity of reduced nitroprusside, [fe(cn)5no .]3-, toward oxygen
publishDate	2007
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00027863_v129_n2_p278_Videla http://hdl.handle.net/20.500.12110/paper_00027863_v129_n2_p278_Videla
_version_	1768545951890276352

Reactivity of reduced nitroprusside, [Fe(CN)5NO .]3-, toward oxygen

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