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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/46699
Ver los metadatos del registro completo
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CONICET Digital (CONICET) |
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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) |
collection |
CONICET Digital (CONICET) |
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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1844614475657773056 |
score |
13.070432 |