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
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/74019

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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling 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
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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)
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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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