Nitrosyl-Centered Redox and Acid–Base Interconversions in [Ru(Me 3 [9]aneN 3 )(bpy)(NO)] 3,2,1+ . The p K a of HNO for its Nitroxyl Derivative in Aqueous Solution

Autores
Osa Codesido, Nicolas; Weyhermuller, Thomas; Olabe Iparraguirre, Jose Antonio; Slep, Leonardo Daniel
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
This work reports the preparation of a new 6-coordinated nitrosyl compound and its use as a model to explore the redox and acid–base properties of the three redox states of bound nitrosyl (formally NO+, NO•, NO–/HNO) in {RuNO}6,7,8 species. We prepared the octahedral {RuNO}6 complex [Ru(Me3[9]aneN3)(bpy)(NO)]3+ (Me3[9]aneN3: 1,4,7-trimethyl-1,4,7-triazacyclononane; bpy = 2,2′-bipyridine), and the related [Ru(Me3[9]aneN3)(bpy)(NO2)]+ nitro derivative. The compounds were characterized by chemical analysis, X-ray diffraction, NMR, IR, and UV–vis spectroscopies, cyclic voltammetry (CV), UV–vis/IR spectroelectrochemistry, and theoretical calculations (DFT, (TD)DFT). The reaction kinetics between the {RuNO}6 complex and the nucleophile OH– is also presented. The incorporation of tridentate and bidentate ligands in the coordination sphere prevents labilization issues associated with the trans effect when attaining the reduced states of the nitrosyl group. This allows for a consistent interpretation of the changes in the main geometrical parameters: Ru–N and N–O distances, Ru–N–O angle, and the νNO frequency and electronic transitions. We explore the redox properties in acetonitrile and aqueous solutions, and provide a potential (E1/2) − pH (Pourbaix) diagram for the three diatomic nitrosyl-bound species, as well as for HNO and NO2–, including the report of the pKa of the [Ru(Me3[9]aneN3)(bpy)(HNO)]2+ ion, 9.78 ± 0.15 at 25.0 °C.
Fil: Osa Codesido, Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Weyhermuller, Thomas. Max Planck Institute For Chemical Energy Conversion; Alemania
Fil: Olabe Iparraguirre, Jose Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Slep, Leonardo Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Materia
Nitrosyl
Nitroxyl
Structure
Redox And Acid-Base Properties
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/46699

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network_name_str CONICET Digital (CONICET)
spelling Nitrosyl-Centered Redox and Acid–Base Interconversions in [Ru(Me 3 [9]aneN 3 )(bpy)(NO)] 3,2,1+ . The p K a of HNO for its Nitroxyl Derivative in Aqueous SolutionOsa Codesido, NicolasWeyhermuller, ThomasOlabe Iparraguirre, Jose AntonioSlep, Leonardo DanielNitrosylNitroxylStructureRedox And Acid-Base Propertieshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1This work reports the preparation of a new 6-coordinated nitrosyl compound and its use as a model to explore the redox and acid–base properties of the three redox states of bound nitrosyl (formally NO+, NO•, NO–/HNO) in {RuNO}6,7,8 species. We prepared the octahedral {RuNO}6 complex [Ru(Me3[9]aneN3)(bpy)(NO)]3+ (Me3[9]aneN3: 1,4,7-trimethyl-1,4,7-triazacyclononane; bpy = 2,2′-bipyridine), and the related [Ru(Me3[9]aneN3)(bpy)(NO2)]+ nitro derivative. The compounds were characterized by chemical analysis, X-ray diffraction, NMR, IR, and UV–vis spectroscopies, cyclic voltammetry (CV), UV–vis/IR spectroelectrochemistry, and theoretical calculations (DFT, (TD)DFT). The reaction kinetics between the {RuNO}6 complex and the nucleophile OH– is also presented. The incorporation of tridentate and bidentate ligands in the coordination sphere prevents labilization issues associated with the trans effect when attaining the reduced states of the nitrosyl group. This allows for a consistent interpretation of the changes in the main geometrical parameters: Ru–N and N–O distances, Ru–N–O angle, and the νNO frequency and electronic transitions. We explore the redox properties in acetonitrile and aqueous solutions, and provide a potential (E1/2) − pH (Pourbaix) diagram for the three diatomic nitrosyl-bound species, as well as for HNO and NO2–, including the report of the pKa of the [Ru(Me3[9]aneN3)(bpy)(HNO)]2+ ion, 9.78 ± 0.15 at 25.0 °C.Fil: Osa Codesido, Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Weyhermuller, Thomas. Max Planck Institute For Chemical Energy Conversion; AlemaniaFil: Olabe Iparraguirre, Jose Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Slep, Leonardo Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaAmerican Chemical Society2014-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/46699Osa Codesido, Nicolas; Weyhermuller, Thomas; Olabe Iparraguirre, Jose Antonio; Slep, Leonardo Daniel; Nitrosyl-Centered Redox and Acid–Base Interconversions in [Ru(Me 3 [9]aneN 3 )(bpy)(NO)] 3,2,1+ . The p K a of HNO for its Nitroxyl Derivative in Aqueous Solution; American Chemical Society; Inorganic Chemistry; 53; 2; 1-2014; 981-9970020-1669CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/pdf/10.1021/ic402448pinfo:eu-repo/semantics/altIdentifier/doi/10.1021/ic402448pinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:43:57Zoai:ri.conicet.gov.ar:11336/46699instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:43:57.52CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Nitrosyl-Centered Redox and Acid–Base Interconversions in [Ru(Me 3 [9]aneN 3 )(bpy)(NO)] 3,2,1+ . The p K a of HNO for its Nitroxyl Derivative in Aqueous Solution
title Nitrosyl-Centered Redox and Acid–Base Interconversions in [Ru(Me 3 [9]aneN 3 )(bpy)(NO)] 3,2,1+ . The p K a of HNO for its Nitroxyl Derivative in Aqueous Solution
spellingShingle Nitrosyl-Centered Redox and Acid–Base Interconversions in [Ru(Me 3 [9]aneN 3 )(bpy)(NO)] 3,2,1+ . The p K a of HNO for its Nitroxyl Derivative in Aqueous Solution
Osa Codesido, Nicolas
Nitrosyl
Nitroxyl
Structure
Redox And Acid-Base Properties
title_short Nitrosyl-Centered Redox and Acid–Base Interconversions in [Ru(Me 3 [9]aneN 3 )(bpy)(NO)] 3,2,1+ . The p K a of HNO for its Nitroxyl Derivative in Aqueous Solution
title_full Nitrosyl-Centered Redox and Acid–Base Interconversions in [Ru(Me 3 [9]aneN 3 )(bpy)(NO)] 3,2,1+ . The p K a of HNO for its Nitroxyl Derivative in Aqueous Solution
title_fullStr Nitrosyl-Centered Redox and Acid–Base Interconversions in [Ru(Me 3 [9]aneN 3 )(bpy)(NO)] 3,2,1+ . The p K a of HNO for its Nitroxyl Derivative in Aqueous Solution
title_full_unstemmed Nitrosyl-Centered Redox and Acid–Base Interconversions in [Ru(Me 3 [9]aneN 3 )(bpy)(NO)] 3,2,1+ . The p K a of HNO for its Nitroxyl Derivative in Aqueous Solution
title_sort Nitrosyl-Centered Redox and Acid–Base Interconversions in [Ru(Me 3 [9]aneN 3 )(bpy)(NO)] 3,2,1+ . The p K a of HNO for its Nitroxyl Derivative in Aqueous Solution
dc.creator.none.fl_str_mv Osa Codesido, Nicolas
Weyhermuller, Thomas
Olabe Iparraguirre, Jose Antonio
Slep, Leonardo Daniel
author Osa Codesido, Nicolas
author_facet Osa Codesido, Nicolas
Weyhermuller, Thomas
Olabe Iparraguirre, Jose Antonio
Slep, Leonardo Daniel
author_role author
author2 Weyhermuller, Thomas
Olabe Iparraguirre, Jose Antonio
Slep, Leonardo Daniel
author2_role author
author
author
dc.subject.none.fl_str_mv Nitrosyl
Nitroxyl
Structure
Redox And Acid-Base Properties
topic Nitrosyl
Nitroxyl
Structure
Redox And Acid-Base Properties
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv This work reports the preparation of a new 6-coordinated nitrosyl compound and its use as a model to explore the redox and acid–base properties of the three redox states of bound nitrosyl (formally NO+, NO•, NO–/HNO) in {RuNO}6,7,8 species. We prepared the octahedral {RuNO}6 complex [Ru(Me3[9]aneN3)(bpy)(NO)]3+ (Me3[9]aneN3: 1,4,7-trimethyl-1,4,7-triazacyclononane; bpy = 2,2′-bipyridine), and the related [Ru(Me3[9]aneN3)(bpy)(NO2)]+ nitro derivative. The compounds were characterized by chemical analysis, X-ray diffraction, NMR, IR, and UV–vis spectroscopies, cyclic voltammetry (CV), UV–vis/IR spectroelectrochemistry, and theoretical calculations (DFT, (TD)DFT). The reaction kinetics between the {RuNO}6 complex and the nucleophile OH– is also presented. The incorporation of tridentate and bidentate ligands in the coordination sphere prevents labilization issues associated with the trans effect when attaining the reduced states of the nitrosyl group. This allows for a consistent interpretation of the changes in the main geometrical parameters: Ru–N and N–O distances, Ru–N–O angle, and the νNO frequency and electronic transitions. We explore the redox properties in acetonitrile and aqueous solutions, and provide a potential (E1/2) − pH (Pourbaix) diagram for the three diatomic nitrosyl-bound species, as well as for HNO and NO2–, including the report of the pKa of the [Ru(Me3[9]aneN3)(bpy)(HNO)]2+ ion, 9.78 ± 0.15 at 25.0 °C.
Fil: Osa Codesido, Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Weyhermuller, Thomas. Max Planck Institute For Chemical Energy Conversion; Alemania
Fil: Olabe Iparraguirre, Jose Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Slep, Leonardo Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
description This work reports the preparation of a new 6-coordinated nitrosyl compound and its use as a model to explore the redox and acid–base properties of the three redox states of bound nitrosyl (formally NO+, NO•, NO–/HNO) in {RuNO}6,7,8 species. We prepared the octahedral {RuNO}6 complex [Ru(Me3[9]aneN3)(bpy)(NO)]3+ (Me3[9]aneN3: 1,4,7-trimethyl-1,4,7-triazacyclononane; bpy = 2,2′-bipyridine), and the related [Ru(Me3[9]aneN3)(bpy)(NO2)]+ nitro derivative. The compounds were characterized by chemical analysis, X-ray diffraction, NMR, IR, and UV–vis spectroscopies, cyclic voltammetry (CV), UV–vis/IR spectroelectrochemistry, and theoretical calculations (DFT, (TD)DFT). The reaction kinetics between the {RuNO}6 complex and the nucleophile OH– is also presented. The incorporation of tridentate and bidentate ligands in the coordination sphere prevents labilization issues associated with the trans effect when attaining the reduced states of the nitrosyl group. This allows for a consistent interpretation of the changes in the main geometrical parameters: Ru–N and N–O distances, Ru–N–O angle, and the νNO frequency and electronic transitions. We explore the redox properties in acetonitrile and aqueous solutions, and provide a potential (E1/2) − pH (Pourbaix) diagram for the three diatomic nitrosyl-bound species, as well as for HNO and NO2–, including the report of the pKa of the [Ru(Me3[9]aneN3)(bpy)(HNO)]2+ ion, 9.78 ± 0.15 at 25.0 °C.
publishDate 2014
dc.date.none.fl_str_mv 2014-01
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/46699
Osa Codesido, Nicolas; Weyhermuller, Thomas; Olabe Iparraguirre, Jose Antonio; Slep, Leonardo Daniel; Nitrosyl-Centered Redox and Acid–Base Interconversions in [Ru(Me 3 [9]aneN 3 )(bpy)(NO)] 3,2,1+ . The p K a of HNO for its Nitroxyl Derivative in Aqueous Solution; American Chemical Society; Inorganic Chemistry; 53; 2; 1-2014; 981-997
0020-1669
CONICET Digital
CONICET
url http://hdl.handle.net/11336/46699
identifier_str_mv Osa Codesido, Nicolas; Weyhermuller, Thomas; Olabe Iparraguirre, Jose Antonio; Slep, Leonardo Daniel; Nitrosyl-Centered Redox and Acid–Base Interconversions in [Ru(Me 3 [9]aneN 3 )(bpy)(NO)] 3,2,1+ . The p K a of HNO for its Nitroxyl Derivative in Aqueous Solution; American Chemical Society; Inorganic Chemistry; 53; 2; 1-2014; 981-997
0020-1669
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/pdf/10.1021/ic402448p
info:eu-repo/semantics/altIdentifier/doi/10.1021/ic402448p
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
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instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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