Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies
- Autores
- Singh, Priti; Das, Atanu Kumar; Sarkar, Biprajit; Niemeyer, Mark; Roncaroli, Federico; Olabe Iparraguirre, Jose Antonio; Fiedler, Jan; Zális, Stanislav; Kaim, Wolfgang
- Año de publicación
- 2008
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- Experimental and computational results for different ruthenium nitrosyl porphyrin complexes [(Por)Ru(NO)(X)]n+ (where Por2- = tetraphenylporphyrin dianion (TPP2-) or octaethylporphyrin dianion (OEP2-) and X = H2O (n = 1,2,3) or pyridine, 4-cyanopyridine, or 4-N,N-dimethylaminopyridine (n = 1,0)) are reported with respect to their electron-transfer behavior. The structure of [(TPP)Ru(NO)(H2O)]BF4 is established as an {MNO} 6 species with an almost-linear RuNO arrangement at 178.1(3)°. The compound [(Por)Ru(NO)(H2O)]BF4 undergoes two reversible one-electron oxidation processes. Spectroelectrochemical measurements (IR, UV-vis-NIR, and EPR) indicate that the first oxidation occurs on the porphyrin ring, as evident from the appearance of diagnostic porphyrin radical-anion vibrational bands (1530 cm-1 for OEP•- and 1290 cm-1 for TPP•-), from the small shift of ∼20 cm-1 for νNO and from the EPR signal at g iso ≈ 2.00. The second oxidation, which was found to be electrochemically reversible for the OEP compound, shows a 55 cm-1 shift in νNO, suggesting a partially metal-centered process. The compounds [(Por)Ru(NO)(X)]BF4, where X = pyridines, undergo a reversible one-electron reduction. The site of the reduction was determined by spectroelectrochemical studies to be NO-centered with a ca. -300 cm-1 shift in νNO. The EPR response of the NO• complexes was essentially unaffected by the variation in the substituted pyridines X. DFT calculations support the interpretation of the experimental results because the HOMO of [(TPP)Ru(NO)(X)]+, where X = H 2O or pyridines, was calculated to be centered at the porphyrin π system, whereas the LUMO of [(TPP)Ru(NO)(X)]+ has about 50% π*(NO) character. This confirms that the (first) oxidation of [(Por)Ru(NO)(H2O)]+ occurs on the porphyrin ring wheras the reduction of [(Por)Ru(NO)(X)]+ is largely NO-centered with the metal remaining in the low-spin ruthenium(II) state throughout. The 4% pyridine contribution to the LUMO of [(TPP)Ru(NO)(py)]+ is correlated with the stability of the reduced form as opposed to that of the aqua complex.
Fil: Singh, Priti. Universität Stuttgart; Alemania
Fil: Das, Atanu Kumar. Universität Stuttgart; Alemania
Fil: Sarkar, Biprajit. Universität Stuttgart; Alemania
Fil: Niemeyer, Mark. Universität Stuttgart; Alemania
Fil: Roncaroli, Federico. 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: 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: Fiedler, Jan. Czech Academy of Sciences. J. Heyrovsky Institute of Physical Chemistry; República Checa
Fil: Zális, Stanislav. Czech Academy of Sciences. J. Heyrovsky Institute of Physical Chemistry; República Checa
Fil: Kaim, Wolfgang. Universität Stuttgart; Alemania - Materia
-
Ruthenium
Nitrosyl
Porphyrins - 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:11336/74019
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Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studiesSingh, PritiDas, Atanu KumarSarkar, BiprajitNiemeyer, MarkRoncaroli, FedericoOlabe Iparraguirre, Jose AntonioFiedler, JanZális, StanislavKaim, WolfgangRutheniumNitrosylPorphyrinshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Experimental and computational results for different ruthenium nitrosyl porphyrin complexes [(Por)Ru(NO)(X)]n+ (where Por2- = tetraphenylporphyrin dianion (TPP2-) or octaethylporphyrin dianion (OEP2-) and X = H2O (n = 1,2,3) or pyridine, 4-cyanopyridine, or 4-N,N-dimethylaminopyridine (n = 1,0)) are reported with respect to their electron-transfer behavior. The structure of [(TPP)Ru(NO)(H2O)]BF4 is established as an {MNO} 6 species with an almost-linear RuNO arrangement at 178.1(3)°. The compound [(Por)Ru(NO)(H2O)]BF4 undergoes two reversible one-electron oxidation processes. Spectroelectrochemical measurements (IR, UV-vis-NIR, and EPR) indicate that the first oxidation occurs on the porphyrin ring, as evident from the appearance of diagnostic porphyrin radical-anion vibrational bands (1530 cm-1 for OEP•- and 1290 cm-1 for TPP•-), from the small shift of ∼20 cm-1 for νNO and from the EPR signal at g iso ≈ 2.00. The second oxidation, which was found to be electrochemically reversible for the OEP compound, shows a 55 cm-1 shift in νNO, suggesting a partially metal-centered process. The compounds [(Por)Ru(NO)(X)]BF4, where X = pyridines, undergo a reversible one-electron reduction. The site of the reduction was determined by spectroelectrochemical studies to be NO-centered with a ca. -300 cm-1 shift in νNO. The EPR response of the NO• complexes was essentially unaffected by the variation in the substituted pyridines X. DFT calculations support the interpretation of the experimental results because the HOMO of [(TPP)Ru(NO)(X)]+, where X = H 2O or pyridines, was calculated to be centered at the porphyrin π system, whereas the LUMO of [(TPP)Ru(NO)(X)]+ has about 50% π*(NO) character. This confirms that the (first) oxidation of [(Por)Ru(NO)(H2O)]+ occurs on the porphyrin ring wheras the reduction of [(Por)Ru(NO)(X)]+ is largely NO-centered with the metal remaining in the low-spin ruthenium(II) state throughout. The 4% pyridine contribution to the LUMO of [(TPP)Ru(NO)(py)]+ is correlated with the stability of the reduced form as opposed to that of the aqua complex.Fil: Singh, Priti. Universität Stuttgart; AlemaniaFil: Das, Atanu Kumar. Universität Stuttgart; AlemaniaFil: Sarkar, Biprajit. Universität Stuttgart; AlemaniaFil: Niemeyer, Mark. Universität Stuttgart; AlemaniaFil: Roncaroli, Federico. 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: 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: Fiedler, Jan. Czech Academy of Sciences. J. Heyrovsky Institute of Physical Chemistry; República ChecaFil: Zális, Stanislav. Czech Academy of Sciences. J. Heyrovsky Institute of Physical Chemistry; República ChecaFil: Kaim, Wolfgang. Universität Stuttgart; AlemaniaAmerican Chemical Society2008-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/74019Singh, Priti; Das, Atanu Kumar; Sarkar, Biprajit; Niemeyer, Mark; Roncaroli, Federico; et al.; Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies; American Chemical Society; Inorganic Chemistry; 47; 16; 8-2008; 7106-71130020-1669CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/ic702371tinfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ic702371tinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:49:13Zoai:ri.conicet.gov.ar:11336/74019instacron: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 09:49:13.858CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies |
title |
Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies |
spellingShingle |
Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies Singh, Priti Ruthenium Nitrosyl Porphyrins |
title_short |
Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies |
title_full |
Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies |
title_fullStr |
Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies |
title_full_unstemmed |
Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies |
title_sort |
Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies |
dc.creator.none.fl_str_mv |
Singh, Priti Das, Atanu Kumar Sarkar, Biprajit Niemeyer, Mark Roncaroli, Federico Olabe Iparraguirre, Jose Antonio Fiedler, Jan Zális, Stanislav Kaim, Wolfgang |
author |
Singh, Priti |
author_facet |
Singh, Priti Das, Atanu Kumar Sarkar, Biprajit Niemeyer, Mark Roncaroli, Federico Olabe Iparraguirre, Jose Antonio Fiedler, Jan Zális, Stanislav Kaim, Wolfgang |
author_role |
author |
author2 |
Das, Atanu Kumar Sarkar, Biprajit Niemeyer, Mark Roncaroli, Federico Olabe Iparraguirre, Jose Antonio Fiedler, Jan Zális, Stanislav Kaim, Wolfgang |
author2_role |
author author author author author author author author |
dc.subject.none.fl_str_mv |
Ruthenium Nitrosyl Porphyrins |
topic |
Ruthenium Nitrosyl Porphyrins |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
Experimental and computational results for different ruthenium nitrosyl porphyrin complexes [(Por)Ru(NO)(X)]n+ (where Por2- = tetraphenylporphyrin dianion (TPP2-) or octaethylporphyrin dianion (OEP2-) and X = H2O (n = 1,2,3) or pyridine, 4-cyanopyridine, or 4-N,N-dimethylaminopyridine (n = 1,0)) are reported with respect to their electron-transfer behavior. The structure of [(TPP)Ru(NO)(H2O)]BF4 is established as an {MNO} 6 species with an almost-linear RuNO arrangement at 178.1(3)°. The compound [(Por)Ru(NO)(H2O)]BF4 undergoes two reversible one-electron oxidation processes. Spectroelectrochemical measurements (IR, UV-vis-NIR, and EPR) indicate that the first oxidation occurs on the porphyrin ring, as evident from the appearance of diagnostic porphyrin radical-anion vibrational bands (1530 cm-1 for OEP•- and 1290 cm-1 for TPP•-), from the small shift of ∼20 cm-1 for νNO and from the EPR signal at g iso ≈ 2.00. The second oxidation, which was found to be electrochemically reversible for the OEP compound, shows a 55 cm-1 shift in νNO, suggesting a partially metal-centered process. The compounds [(Por)Ru(NO)(X)]BF4, where X = pyridines, undergo a reversible one-electron reduction. The site of the reduction was determined by spectroelectrochemical studies to be NO-centered with a ca. -300 cm-1 shift in νNO. The EPR response of the NO• complexes was essentially unaffected by the variation in the substituted pyridines X. DFT calculations support the interpretation of the experimental results because the HOMO of [(TPP)Ru(NO)(X)]+, where X = H 2O or pyridines, was calculated to be centered at the porphyrin π system, whereas the LUMO of [(TPP)Ru(NO)(X)]+ has about 50% π*(NO) character. This confirms that the (first) oxidation of [(Por)Ru(NO)(H2O)]+ occurs on the porphyrin ring wheras the reduction of [(Por)Ru(NO)(X)]+ is largely NO-centered with the metal remaining in the low-spin ruthenium(II) state throughout. The 4% pyridine contribution to the LUMO of [(TPP)Ru(NO)(py)]+ is correlated with the stability of the reduced form as opposed to that of the aqua complex. Fil: Singh, Priti. Universität Stuttgart; Alemania Fil: Das, Atanu Kumar. Universität Stuttgart; Alemania Fil: Sarkar, Biprajit. Universität Stuttgart; Alemania Fil: Niemeyer, Mark. Universität Stuttgart; Alemania Fil: Roncaroli, Federico. 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: 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: Fiedler, Jan. Czech Academy of Sciences. J. Heyrovsky Institute of Physical Chemistry; República Checa Fil: Zális, Stanislav. Czech Academy of Sciences. J. Heyrovsky Institute of Physical Chemistry; República Checa Fil: Kaim, Wolfgang. Universität Stuttgart; Alemania |
description |
Experimental and computational results for different ruthenium nitrosyl porphyrin complexes [(Por)Ru(NO)(X)]n+ (where Por2- = tetraphenylporphyrin dianion (TPP2-) or octaethylporphyrin dianion (OEP2-) and X = H2O (n = 1,2,3) or pyridine, 4-cyanopyridine, or 4-N,N-dimethylaminopyridine (n = 1,0)) are reported with respect to their electron-transfer behavior. The structure of [(TPP)Ru(NO)(H2O)]BF4 is established as an {MNO} 6 species with an almost-linear RuNO arrangement at 178.1(3)°. The compound [(Por)Ru(NO)(H2O)]BF4 undergoes two reversible one-electron oxidation processes. Spectroelectrochemical measurements (IR, UV-vis-NIR, and EPR) indicate that the first oxidation occurs on the porphyrin ring, as evident from the appearance of diagnostic porphyrin radical-anion vibrational bands (1530 cm-1 for OEP•- and 1290 cm-1 for TPP•-), from the small shift of ∼20 cm-1 for νNO and from the EPR signal at g iso ≈ 2.00. The second oxidation, which was found to be electrochemically reversible for the OEP compound, shows a 55 cm-1 shift in νNO, suggesting a partially metal-centered process. The compounds [(Por)Ru(NO)(X)]BF4, where X = pyridines, undergo a reversible one-electron reduction. The site of the reduction was determined by spectroelectrochemical studies to be NO-centered with a ca. -300 cm-1 shift in νNO. The EPR response of the NO• complexes was essentially unaffected by the variation in the substituted pyridines X. DFT calculations support the interpretation of the experimental results because the HOMO of [(TPP)Ru(NO)(X)]+, where X = H 2O or pyridines, was calculated to be centered at the porphyrin π system, whereas the LUMO of [(TPP)Ru(NO)(X)]+ has about 50% π*(NO) character. This confirms that the (first) oxidation of [(Por)Ru(NO)(H2O)]+ occurs on the porphyrin ring wheras the reduction of [(Por)Ru(NO)(X)]+ is largely NO-centered with the metal remaining in the low-spin ruthenium(II) state throughout. The 4% pyridine contribution to the LUMO of [(TPP)Ru(NO)(py)]+ is correlated with the stability of the reduced form as opposed to that of the aqua complex. |
publishDate |
2008 |
dc.date.none.fl_str_mv |
2008-08 |
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/11336/74019 Singh, Priti; Das, Atanu Kumar; Sarkar, Biprajit; Niemeyer, Mark; Roncaroli, Federico; et al.; Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies; American Chemical Society; Inorganic Chemistry; 47; 16; 8-2008; 7106-7113 0020-1669 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/74019 |
identifier_str_mv |
Singh, Priti; Das, Atanu Kumar; Sarkar, Biprajit; Niemeyer, Mark; Roncaroli, Federico; et al.; Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies; American Chemical Society; Inorganic Chemistry; 47; 16; 8-2008; 7106-7113 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/doi/10.1021/ic702371t info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ic702371t |
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 |
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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1844613525010382848 |
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13.070432 |