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...

Descripción completa

Guardado en:

Detalles Bibliográficos
Autores principales:	Quiroga, S.L., Almaraz, A.E., Amorebieta, V.T., Perissinotti, L.L., Olabe, J.A.
Formato:	JOUR
Materias:	addition reaction iron N ligands nitrososulfide ligands nitrosyl sulfur Absorbance-time curves Concentration ratio FTIR spectroscopy 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 stereoisomerism ultraviolet spectrophotometry Ferrous Compounds Hydrogen Sulfide Hydrogen-Ion Concentration Kinetics Molecular Structure Nitrogen Oxides Nitroprusside Oxidation-Reduction Spectrophotometry, Ultraviolet Stereoisomerism
Acceso en línea:	http://hdl.handle.net/20.500.12110/paper_09476539_v17_n15_p4145_Quiroga
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	todo:paper_09476539_v17_n15_p4145_Quiroga
record_format	dspace
spelling	todo:paper_09476539_v17_n15_p4145_Quiroga2023-10-03T15:49:26Z Addition and redox reactivity of hydrogen sulfides (H2S/HS -) with nitroprusside: New chemistry of nitrososulfide ligands Quiroga, S.L. Almaraz, A.E. Amorebieta, V.T. Perissinotti, L.L. Olabe, J.A. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar 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 Quiroga, S.L. Almaraz, A.E. Amorebieta, V.T. Perissinotti, L.L. Olabe, J.A. 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.
format	JOUR
author	Quiroga, S.L. Almaraz, A.E. Amorebieta, V.T. Perissinotti, L.L. Olabe, J.A.
author_facet	Quiroga, S.L. Almaraz, A.E. Amorebieta, V.T. Perissinotti, L.L. Olabe, J.A.
author_sort	Quiroga, S.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
url	http://hdl.handle.net/20.500.12110/paper_09476539_v17_n15_p4145_Quiroga
work_keys_str_mv	AT quirogasl additionandredoxreactivityofhydrogensulfidesh2shswithnitroprussidenewchemistryofnitrososulfideligands AT almarazae additionandredoxreactivityofhydrogensulfidesh2shswithnitroprussidenewchemistryofnitrososulfideligands AT amorebietavt additionandredoxreactivityofhydrogensulfidesh2shswithnitroprussidenewchemistryofnitrososulfideligands AT perissinottill additionandredoxreactivityofhydrogensulfidesh2shswithnitroprussidenewchemistryofnitrososulfideligands AT olabeja additionandredoxreactivityofhydrogensulfidesh2shswithnitroprussidenewchemistryofnitrososulfideligands
_version_	1807318899936460800

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

Ejemplares similares