Addition and redox reactivity of hydrogen sulfides (H2S/HS -) with nitroprusside: New chemistry of nitrososulfide ligands

The nitroprusside ion [Fe(CN)5NO]2- (NP) reacts with excess HS- in the pH range 8.5-12.5, in anaerobic medium ("Gmelin" reaction). The progress of the addition process of HS - into the bound NO+ ligand was monitored by stopped-flow UV/Vis/EPR and FTIR spectroscopy, mass spectrometry, and c...

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Autores principales: Perissinotti, Laura L., Olabe Iparraguirre, Jose Antonio
Publicado: 2011
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pH
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_09476539_v17_n15_p4145_Quiroga
http://hdl.handle.net/20.500.12110/paper_09476539_v17_n15_p4145_Quiroga
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spelling paper:paper_09476539_v17_n15_p4145_Quiroga2023-06-08T15:53:57Z Addition and redox reactivity of hydrogen sulfides (H2S/HS -) with nitroprusside: New chemistry of nitrososulfide ligands Perissinotti, Laura L. Olabe Iparraguirre, Jose Antonio addition reaction iron N ligands nitrososulfide ligands nitrosyl sulfur Absorbance-time curves Concentration ratio FTIR spectroscopy N ligands nitrososulfide ligands nitrosyl NO release Nucleophilic attack pH range Reactive intermediate Redox reactivity Reversible process Stopped flow Theoretical calculations Addition reactions Chemical analysis Cyanides Fourier transform infrared spectroscopy Hydraulic structures Hydrogen Mass spectrometry pH Reaction intermediates Reaction kinetics Sulfur Ligands ferrous ion hydrogen sulfide ligand nitrogen oxide nitroprusside sodium article chemical structure chemistry kinetics oxidation reduction reaction pH stereoisomerism ultraviolet spectrophotometry Ferrous Compounds Hydrogen Sulfide Hydrogen-Ion Concentration Kinetics Ligands Molecular Structure Nitrogen Oxides Nitroprusside Oxidation-Reduction Spectrophotometry, Ultraviolet Stereoisomerism The nitroprusside ion [Fe(CN)5NO]2- (NP) reacts with excess HS- in the pH range 8.5-12.5, in anaerobic medium ("Gmelin" reaction). The progress of the addition process of HS - into the bound NO+ ligand was monitored by stopped-flow UV/Vis/EPR and FTIR spectroscopy, mass spectrometry, and chemical analysis. Theoretical calculations were employed for the characterization of the initial adducts and reaction intermediates. The shapes of the absorbance-time curves at 535-575 nm depend on the pH and concentration ratio of the reactants, R=[HS -]/[NP]. The initial adduct [Fe(CN)5N(O)SH]3- (AH, Î max≈570 nm) forms in the course of a reversible process, with kad=190±20 M-1 s-1, k -ad=0.3±0.05 s-1. Deprotonation of AH (pK a=10.5±0.1, at 25.0 °C, I=1 M), leads to [Fe(CN) 5N(O)S]4- (A, Î max=535 nm, ε=6000±300 M-1 cm-1). [Fe(CN) 5NO].3- and HS2. 2- radicals form through the spontaneous decomposition of AH and A. The minor formation of the [Fe(CN)5NO]3- ion equilibrates with [Fe(CN)4NO]2- through cyanide labilization, and generates the "g=2.03" iron-dinitrosyl, [Fe(NO)2(SH) 2]-, which is labile toward NO release. Alternative nucleophilic attack of HS- on AH and A generates the reactive intermediates [Fe(CN)5N(OH)(SH)2]3- and [Fe(CN)5N(OH)(S)(SH)]4-, respectively, which decompose through multielectronic nitrosyl reductions, leading to NH3 and hydrogen disulfide, HS2-. N2O is also produced at pH≥11. Biological relevance relates to the role of NO, NO-, and other bound intermediates, eventually able to be released to the medium and rapidly trapped by substrates. Structure and reactivity comparisons of the new nitrososulfide ligands with free and bound nitrosothiolates are provided. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Fil:Perissinotti, L.L. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Olabe, J.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2011 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_09476539_v17_n15_p4145_Quiroga http://hdl.handle.net/20.500.12110/paper_09476539_v17_n15_p4145_Quiroga
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic addition reaction
iron
N ligands
nitrososulfide ligands
nitrosyl
sulfur
Absorbance-time curves
Concentration ratio
FTIR spectroscopy
N ligands
nitrososulfide ligands
nitrosyl
NO release
Nucleophilic attack
pH range
Reactive intermediate
Redox reactivity
Reversible process
Stopped flow
Theoretical calculations
Addition reactions
Chemical analysis
Cyanides
Fourier transform infrared spectroscopy
Hydraulic structures
Hydrogen
Mass spectrometry
pH
Reaction intermediates
Reaction kinetics
Sulfur
Ligands
ferrous ion
hydrogen sulfide
ligand
nitrogen oxide
nitroprusside sodium
article
chemical structure
chemistry
kinetics
oxidation reduction reaction
pH
stereoisomerism
ultraviolet spectrophotometry
Ferrous Compounds
Hydrogen Sulfide
Hydrogen-Ion Concentration
Kinetics
Ligands
Molecular Structure
Nitrogen Oxides
Nitroprusside
Oxidation-Reduction
Spectrophotometry, Ultraviolet
Stereoisomerism
spellingShingle addition reaction
iron
N ligands
nitrososulfide ligands
nitrosyl
sulfur
Absorbance-time curves
Concentration ratio
FTIR spectroscopy
N ligands
nitrososulfide ligands
nitrosyl
NO release
Nucleophilic attack
pH range
Reactive intermediate
Redox reactivity
Reversible process
Stopped flow
Theoretical calculations
Addition reactions
Chemical analysis
Cyanides
Fourier transform infrared spectroscopy
Hydraulic structures
Hydrogen
Mass spectrometry
pH
Reaction intermediates
Reaction kinetics
Sulfur
Ligands
ferrous ion
hydrogen sulfide
ligand
nitrogen oxide
nitroprusside sodium
article
chemical structure
chemistry
kinetics
oxidation reduction reaction
pH
stereoisomerism
ultraviolet spectrophotometry
Ferrous Compounds
Hydrogen Sulfide
Hydrogen-Ion Concentration
Kinetics
Ligands
Molecular Structure
Nitrogen Oxides
Nitroprusside
Oxidation-Reduction
Spectrophotometry, Ultraviolet
Stereoisomerism
Perissinotti, Laura L.
Olabe Iparraguirre, Jose Antonio
Addition and redox reactivity of hydrogen sulfides (H2S/HS -) with nitroprusside: New chemistry of nitrososulfide ligands
topic_facet addition reaction
iron
N ligands
nitrososulfide ligands
nitrosyl
sulfur
Absorbance-time curves
Concentration ratio
FTIR spectroscopy
N ligands
nitrososulfide ligands
nitrosyl
NO release
Nucleophilic attack
pH range
Reactive intermediate
Redox reactivity
Reversible process
Stopped flow
Theoretical calculations
Addition reactions
Chemical analysis
Cyanides
Fourier transform infrared spectroscopy
Hydraulic structures
Hydrogen
Mass spectrometry
pH
Reaction intermediates
Reaction kinetics
Sulfur
Ligands
ferrous ion
hydrogen sulfide
ligand
nitrogen oxide
nitroprusside sodium
article
chemical structure
chemistry
kinetics
oxidation reduction reaction
pH
stereoisomerism
ultraviolet spectrophotometry
Ferrous Compounds
Hydrogen Sulfide
Hydrogen-Ion Concentration
Kinetics
Ligands
Molecular Structure
Nitrogen Oxides
Nitroprusside
Oxidation-Reduction
Spectrophotometry, Ultraviolet
Stereoisomerism
description The nitroprusside ion [Fe(CN)5NO]2- (NP) reacts with excess HS- in the pH range 8.5-12.5, in anaerobic medium ("Gmelin" reaction). The progress of the addition process of HS - into the bound NO+ ligand was monitored by stopped-flow UV/Vis/EPR and FTIR spectroscopy, mass spectrometry, and chemical analysis. Theoretical calculations were employed for the characterization of the initial adducts and reaction intermediates. The shapes of the absorbance-time curves at 535-575 nm depend on the pH and concentration ratio of the reactants, R=[HS -]/[NP]. The initial adduct [Fe(CN)5N(O)SH]3- (AH, Î max≈570 nm) forms in the course of a reversible process, with kad=190±20 M-1 s-1, k -ad=0.3±0.05 s-1. Deprotonation of AH (pK a=10.5±0.1, at 25.0 °C, I=1 M), leads to [Fe(CN) 5N(O)S]4- (A, Î max=535 nm, ε=6000±300 M-1 cm-1). [Fe(CN) 5NO].3- and HS2. 2- radicals form through the spontaneous decomposition of AH and A. The minor formation of the [Fe(CN)5NO]3- ion equilibrates with [Fe(CN)4NO]2- through cyanide labilization, and generates the "g=2.03" iron-dinitrosyl, [Fe(NO)2(SH) 2]-, which is labile toward NO release. Alternative nucleophilic attack of HS- on AH and A generates the reactive intermediates [Fe(CN)5N(OH)(SH)2]3- and [Fe(CN)5N(OH)(S)(SH)]4-, respectively, which decompose through multielectronic nitrosyl reductions, leading to NH3 and hydrogen disulfide, HS2-. N2O is also produced at pH≥11. Biological relevance relates to the role of NO, NO-, and other bound intermediates, eventually able to be released to the medium and rapidly trapped by substrates. Structure and reactivity comparisons of the new nitrososulfide ligands with free and bound nitrosothiolates are provided. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
author Perissinotti, Laura L.
Olabe Iparraguirre, Jose Antonio
author_facet Perissinotti, Laura L.
Olabe Iparraguirre, Jose Antonio
author_sort Perissinotti, Laura L.
title Addition and redox reactivity of hydrogen sulfides (H2S/HS -) with nitroprusside: New chemistry of nitrososulfide ligands
title_short Addition and redox reactivity of hydrogen sulfides (H2S/HS -) with nitroprusside: New chemistry of nitrososulfide ligands
title_full Addition and redox reactivity of hydrogen sulfides (H2S/HS -) with nitroprusside: New chemistry of nitrososulfide ligands
title_fullStr Addition and redox reactivity of hydrogen sulfides (H2S/HS -) with nitroprusside: New chemistry of nitrososulfide ligands
title_full_unstemmed Addition and redox reactivity of hydrogen sulfides (H2S/HS -) with nitroprusside: New chemistry of nitrososulfide ligands
title_sort addition and redox reactivity of hydrogen sulfides (h2s/hs -) with nitroprusside: new chemistry of nitrososulfide ligands
publishDate 2011
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_09476539_v17_n15_p4145_Quiroga
http://hdl.handle.net/20.500.12110/paper_09476539_v17_n15_p4145_Quiroga
work_keys_str_mv AT perissinottilaural additionandredoxreactivityofhydrogensulfidesh2shswithnitroprussidenewchemistryofnitrososulfideligands
AT olabeiparraguirrejoseantonio additionandredoxreactivityofhydrogensulfidesh2shswithnitroprussidenewchemistryofnitrososulfideligands
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