Mixed-valency with cyanides as terminal ligands: Diruthenium(III,II) complexes with the 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine bridge and variable co-ligands (CN- vs. bpy or NH3)

Autores
Vergara, Monica Mercedes; García Posse, Mónica Ema; Fagalde, Florencia; Katz, Néstor Eduardo; Fiedler, Jan; Sarkar, Biprajit; Sieger, Sabine; Kaim, Wolfgang
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
New diruthenium complexes (PPN)4[(NC)4Ru(μ-bptz)Ru(CN)4], (PPN)4 1, and [(bpy)2Ru(μ-bptz)Ru(CN)4], 2, (PPN+ = bis(triphenylphospine)iminium; bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine; bpy = 2,2′-bipyridine), were synthesised and characterised by spectroscopic and electrochemical techniques. The comproportionation constant Kc = 107.0 of the mixed-valent species [(NC)4Ru(μ-bptz)Ru(CN)4]3- as obtained by oxidation of 14- in CH3CN is much lower than the Kc = 1015.0 previously detected for [(H3N)4Ru(bptz)Ru(NH3)4]5+, reflecting the competition between CN- and bptz for the π-electron density of the metals. Comparison with several other bptz-bridged diruthenium(II,III) complexes reveals an approximate correlation between Kc and the diminishing effective π acceptor capacity of the ancillary terminal ligands. In addition to the intense MLCT absorption at λmax = 624 nm, the main IVCT (intervalence charge transfer) band of 13- was detected by spectroelectrochemistry at λmax = 1695 nm (in CH3CN; ε = 3200 M-1 cm-1). The experimental band width at half-height, Δν1/2 = 2700 cm-1, is slightly smaller than the theoretical value Δν1/2 = 3660 cm-1, calculated from the Hush approximation for Class II mixed-valent species. In agreement with comparatively moderate metal-metal coupling, the mixed-valent intermediate 13- was found to be EPR silent even at 4 K. The unsymmetrical mixed-valent complex [(bpy)2RuII(μ-bptz)RuIII(CN)4]+, obtained in situ by bromine oxidation of 2 in CH3CN/H2O, displays a broad NIR absorption originating from an IVCT transition at λmax = 1075 nm (ε ≈ 1000 M-1 cm-1, Δν1/2 ≈ 4000 cm-1). In addition, the lifetime of the excited-state of the mononuclear precursor complex [Ru(bptz)(CN)4]2- was measured in H2O by laser flash photolysis; the obtained value of τ = 19.6 ns reveals that bptz induces a metal-to-ligand electronic delocalisation effect intermediate between that induced by bpy and bpz (bpz = 2,2′-bipyrazine) in analogous tetracyanoruthenium complexes.
Fil: Vergara, Monica Mercedes. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: García Posse, Mónica Ema. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Fagalde, Florencia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Katz, Néstor Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Fiedler, Jan. Academy of Sciences of the Czech Republic; República Checa
Fil: Sarkar, Biprajit. Universität Stuttgart; Alemania
Fil: Sieger, Sabine. Universität Stuttgart; Alemania
Fil: Kaim, Wolfgang. Universität Stuttgart; Alemania
Materia
Cyano Ligands
Mixed-Valency
Ruthenium Complexes
Spectroelectrochemistry
Tetrazine Ligand
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:11336/52922
Acceder
id CONICETDig_4edecbcf85651d8284630ee870d33233
oai_identifier_str oai:ri.conicet.gov.ar:11336/52922
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Mixed-valency with cyanides as terminal ligands: Diruthenium(III,II) complexes with the 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine bridge and variable co-ligands (CN- vs. bpy or NH3)Vergara, Monica MercedesGarcía Posse, Mónica EmaFagalde, FlorenciaKatz, Néstor EduardoFiedler, JanSarkar, BiprajitSieger, SabineKaim, WolfgangCyano LigandsMixed-ValencyRuthenium ComplexesSpectroelectrochemistryTetrazine Ligandhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1New diruthenium complexes (PPN)4[(NC)4Ru(μ-bptz)Ru(CN)4], (PPN)4 1, and [(bpy)2Ru(μ-bptz)Ru(CN)4], 2, (PPN+ = bis(triphenylphospine)iminium; bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine; bpy = 2,2′-bipyridine), were synthesised and characterised by spectroscopic and electrochemical techniques. The comproportionation constant Kc = 107.0 of the mixed-valent species [(NC)4Ru(μ-bptz)Ru(CN)4]3- as obtained by oxidation of 14- in CH3CN is much lower than the Kc = 1015.0 previously detected for [(H3N)4Ru(bptz)Ru(NH3)4]5+, reflecting the competition between CN- and bptz for the π-electron density of the metals. Comparison with several other bptz-bridged diruthenium(II,III) complexes reveals an approximate correlation between Kc and the diminishing effective π acceptor capacity of the ancillary terminal ligands. In addition to the intense MLCT absorption at λmax = 624 nm, the main IVCT (intervalence charge transfer) band of 13- was detected by spectroelectrochemistry at λmax = 1695 nm (in CH3CN; ε = 3200 M-1 cm-1). The experimental band width at half-height, Δν1/2 = 2700 cm-1, is slightly smaller than the theoretical value Δν1/2 = 3660 cm-1, calculated from the Hush approximation for Class II mixed-valent species. In agreement with comparatively moderate metal-metal coupling, the mixed-valent intermediate 13- was found to be EPR silent even at 4 K. The unsymmetrical mixed-valent complex [(bpy)2RuII(μ-bptz)RuIII(CN)4]+, obtained in situ by bromine oxidation of 2 in CH3CN/H2O, displays a broad NIR absorption originating from an IVCT transition at λmax = 1075 nm (ε ≈ 1000 M-1 cm-1, Δν1/2 ≈ 4000 cm-1). In addition, the lifetime of the excited-state of the mononuclear precursor complex [Ru(bptz)(CN)4]2- was measured in H2O by laser flash photolysis; the obtained value of τ = 19.6 ns reveals that bptz induces a metal-to-ligand electronic delocalisation effect intermediate between that induced by bpy and bpz (bpz = 2,2′-bipyrazine) in analogous tetracyanoruthenium complexes.Fil: Vergara, Monica Mercedes. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: García Posse, Mónica Ema. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Fagalde, Florencia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Katz, Néstor Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Fiedler, Jan. Academy of Sciences of the Czech Republic; República ChecaFil: Sarkar, Biprajit. Universität Stuttgart; AlemaniaFil: Sieger, Sabine. Universität Stuttgart; AlemaniaFil: Kaim, Wolfgang. Universität Stuttgart; AlemaniaElsevier Science Sa2010-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/52922Vergara, Monica Mercedes; García Posse, Mónica Ema; Fagalde, Florencia; Katz, Néstor Eduardo; Fiedler, Jan; et al.; Mixed-valency with cyanides as terminal ligands: Diruthenium(III,II) complexes with the 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine bridge and variable co-ligands (CN- vs. bpy or NH3); Elsevier Science Sa; Inorganica Chimica Acta; 363; 1; 1-2010; 163-1670020-1693CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.ica.2009.09.018info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0020169309005441info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:59:10Zoai:ri.conicet.gov.ar:11336/52922instacron: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 09:59:11.199CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Mixed-valency with cyanides as terminal ligands: Diruthenium(III,II) complexes with the 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine bridge and variable co-ligands (CN- vs. bpy or NH3)
title Mixed-valency with cyanides as terminal ligands: Diruthenium(III,II) complexes with the 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine bridge and variable co-ligands (CN- vs. bpy or NH3)
spellingShingle Mixed-valency with cyanides as terminal ligands: Diruthenium(III,II) complexes with the 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine bridge and variable co-ligands (CN- vs. bpy or NH3)
Vergara, Monica Mercedes
Cyano Ligands
Mixed-Valency
Ruthenium Complexes
Spectroelectrochemistry
Tetrazine Ligand
title_short Mixed-valency with cyanides as terminal ligands: Diruthenium(III,II) complexes with the 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine bridge and variable co-ligands (CN- vs. bpy or NH3)
title_full Mixed-valency with cyanides as terminal ligands: Diruthenium(III,II) complexes with the 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine bridge and variable co-ligands (CN- vs. bpy or NH3)
title_fullStr Mixed-valency with cyanides as terminal ligands: Diruthenium(III,II) complexes with the 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine bridge and variable co-ligands (CN- vs. bpy or NH3)
title_full_unstemmed Mixed-valency with cyanides as terminal ligands: Diruthenium(III,II) complexes with the 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine bridge and variable co-ligands (CN- vs. bpy or NH3)
title_sort Mixed-valency with cyanides as terminal ligands: Diruthenium(III,II) complexes with the 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine bridge and variable co-ligands (CN- vs. bpy or NH3)
dc.creator.none.fl_str_mv Vergara, Monica Mercedes
García Posse, Mónica Ema
Fagalde, Florencia
Katz, Néstor Eduardo
Fiedler, Jan
Sarkar, Biprajit
Sieger, Sabine
Kaim, Wolfgang
author Vergara, Monica Mercedes
author_facet Vergara, Monica Mercedes
García Posse, Mónica Ema
Fagalde, Florencia
Katz, Néstor Eduardo
Fiedler, Jan
Sarkar, Biprajit
Sieger, Sabine
Kaim, Wolfgang
author_role author
author2 García Posse, Mónica Ema
Fagalde, Florencia
Katz, Néstor Eduardo
Fiedler, Jan
Sarkar, Biprajit
Sieger, Sabine
Kaim, Wolfgang
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Cyano Ligands
Mixed-Valency
Ruthenium Complexes
Spectroelectrochemistry
Tetrazine Ligand
topic Cyano Ligands
Mixed-Valency
Ruthenium Complexes
Spectroelectrochemistry
Tetrazine Ligand
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv New diruthenium complexes (PPN)4[(NC)4Ru(μ-bptz)Ru(CN)4], (PPN)4 1, and [(bpy)2Ru(μ-bptz)Ru(CN)4], 2, (PPN+ = bis(triphenylphospine)iminium; bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine; bpy = 2,2′-bipyridine), were synthesised and characterised by spectroscopic and electrochemical techniques. The comproportionation constant Kc = 107.0 of the mixed-valent species [(NC)4Ru(μ-bptz)Ru(CN)4]3- as obtained by oxidation of 14- in CH3CN is much lower than the Kc = 1015.0 previously detected for [(H3N)4Ru(bptz)Ru(NH3)4]5+, reflecting the competition between CN- and bptz for the π-electron density of the metals. Comparison with several other bptz-bridged diruthenium(II,III) complexes reveals an approximate correlation between Kc and the diminishing effective π acceptor capacity of the ancillary terminal ligands. In addition to the intense MLCT absorption at λmax = 624 nm, the main IVCT (intervalence charge transfer) band of 13- was detected by spectroelectrochemistry at λmax = 1695 nm (in CH3CN; ε = 3200 M-1 cm-1). The experimental band width at half-height, Δν1/2 = 2700 cm-1, is slightly smaller than the theoretical value Δν1/2 = 3660 cm-1, calculated from the Hush approximation for Class II mixed-valent species. In agreement with comparatively moderate metal-metal coupling, the mixed-valent intermediate 13- was found to be EPR silent even at 4 K. The unsymmetrical mixed-valent complex [(bpy)2RuII(μ-bptz)RuIII(CN)4]+, obtained in situ by bromine oxidation of 2 in CH3CN/H2O, displays a broad NIR absorption originating from an IVCT transition at λmax = 1075 nm (ε ≈ 1000 M-1 cm-1, Δν1/2 ≈ 4000 cm-1). In addition, the lifetime of the excited-state of the mononuclear precursor complex [Ru(bptz)(CN)4]2- was measured in H2O by laser flash photolysis; the obtained value of τ = 19.6 ns reveals that bptz induces a metal-to-ligand electronic delocalisation effect intermediate between that induced by bpy and bpz (bpz = 2,2′-bipyrazine) in analogous tetracyanoruthenium complexes.
Fil: Vergara, Monica Mercedes. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: García Posse, Mónica Ema. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Fagalde, Florencia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Katz, Néstor Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Fiedler, Jan. Academy of Sciences of the Czech Republic; República Checa
Fil: Sarkar, Biprajit. Universität Stuttgart; Alemania
Fil: Sieger, Sabine. Universität Stuttgart; Alemania
Fil: Kaim, Wolfgang. Universität Stuttgart; Alemania
description New diruthenium complexes (PPN)4[(NC)4Ru(μ-bptz)Ru(CN)4], (PPN)4 1, and [(bpy)2Ru(μ-bptz)Ru(CN)4], 2, (PPN+ = bis(triphenylphospine)iminium; bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine; bpy = 2,2′-bipyridine), were synthesised and characterised by spectroscopic and electrochemical techniques. The comproportionation constant Kc = 107.0 of the mixed-valent species [(NC)4Ru(μ-bptz)Ru(CN)4]3- as obtained by oxidation of 14- in CH3CN is much lower than the Kc = 1015.0 previously detected for [(H3N)4Ru(bptz)Ru(NH3)4]5+, reflecting the competition between CN- and bptz for the π-electron density of the metals. Comparison with several other bptz-bridged diruthenium(II,III) complexes reveals an approximate correlation between Kc and the diminishing effective π acceptor capacity of the ancillary terminal ligands. In addition to the intense MLCT absorption at λmax = 624 nm, the main IVCT (intervalence charge transfer) band of 13- was detected by spectroelectrochemistry at λmax = 1695 nm (in CH3CN; ε = 3200 M-1 cm-1). The experimental band width at half-height, Δν1/2 = 2700 cm-1, is slightly smaller than the theoretical value Δν1/2 = 3660 cm-1, calculated from the Hush approximation for Class II mixed-valent species. In agreement with comparatively moderate metal-metal coupling, the mixed-valent intermediate 13- was found to be EPR silent even at 4 K. The unsymmetrical mixed-valent complex [(bpy)2RuII(μ-bptz)RuIII(CN)4]+, obtained in situ by bromine oxidation of 2 in CH3CN/H2O, displays a broad NIR absorption originating from an IVCT transition at λmax = 1075 nm (ε ≈ 1000 M-1 cm-1, Δν1/2 ≈ 4000 cm-1). In addition, the lifetime of the excited-state of the mononuclear precursor complex [Ru(bptz)(CN)4]2- was measured in H2O by laser flash photolysis; the obtained value of τ = 19.6 ns reveals that bptz induces a metal-to-ligand electronic delocalisation effect intermediate between that induced by bpy and bpz (bpz = 2,2′-bipyrazine) in analogous tetracyanoruthenium complexes.
publishDate 2010
dc.date.none.fl_str_mv 2010-01
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/11336/52922
Vergara, Monica Mercedes; García Posse, Mónica Ema; Fagalde, Florencia; Katz, Néstor Eduardo; Fiedler, Jan; et al.; Mixed-valency with cyanides as terminal ligands: Diruthenium(III,II) complexes with the 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine bridge and variable co-ligands (CN- vs. bpy or NH3); Elsevier Science Sa; Inorganica Chimica Acta; 363; 1; 1-2010; 163-167
0020-1693
CONICET Digital
CONICET
url http://hdl.handle.net/11336/52922
identifier_str_mv Vergara, Monica Mercedes; García Posse, Mónica Ema; Fagalde, Florencia; Katz, Néstor Eduardo; Fiedler, Jan; et al.; Mixed-valency with cyanides as terminal ligands: Diruthenium(III,II) complexes with the 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine bridge and variable co-ligands (CN- vs. bpy or NH3); Elsevier Science Sa; Inorganica Chimica Acta; 363; 1; 1-2010; 163-167
0020-1693
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.ica.2009.09.018
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0020169309005441
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 Elsevier Science Sa
publisher.none.fl_str_mv Elsevier Science Sa
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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