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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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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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 |
_version_ |
1768546405186535424 |