Photoinduced linkage isomerization in new rhenium(I) tricarbonyl complexes coordinated to N-nitrite and O-nitrite

Autores
Domínguez, Sofía Eugenia; Alborés, Pablo; Fagalde, Florencia
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The ambidentate nitrite ion, NO2−, is a biologically relevant species that can be coordinated to transition metals via the nitrogen or oxygen atom. Most of its physiological effects involve metalloproteins so it is important to understand the factors that control the predominance of one or another isomer. In this work, we present the syntheses and characterization by spectroscopy, electrochemistry and DFT calculations of new rhenium(I) tricarbonyl complexes with different polypyridyl ligands in the coordination sphere and with the nitrite ion coordinated through either its N- or O-atom. For two of them we have determined their crystal structures by X-ray diffraction and we have found that in the solid when the ancilliary ligand is bpy the N-binding mode is the most stable, while dmb is the ligand, the –CH3 substituents imposed the C–H (methyl group)⋯O–NO (nitrito) interactions favoring the O-binding mode. However, at room temperature in CH2Cl2 the nitro isomer is the most stable for both complexes in agreement with DFT calculations. Both complexes exhibit photoinduced linkage isomerism which could be of interesting in the design of new materials. Although nitro complexes are precursors of nitrosyl compounds, in this work the synthesis of the nitrosyl complexes as solid could not be possible because there is higher π-backbonding from Re(I) to the carbonyl groups, or to the polypyridil ligands instead of to the NO group, which is π-acceptor, in consequence the nitrosyl complexes are unstable and decompose immediately to the solvate complexes.
Fil: Domínguez, Sofía Eugenia. 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: Alborés, Pablo. 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: 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
Materia
Nitro
Nitrito
Rhenium (I) Tricarbonyl
Photoinduced Linkage Isomerization
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/30209

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network_name_str CONICET Digital (CONICET)
spelling Photoinduced linkage isomerization in new rhenium(I) tricarbonyl complexes coordinated to N-nitrite and O-nitriteDomínguez, Sofía EugeniaAlborés, PabloFagalde, FlorenciaNitroNitritoRhenium (I) TricarbonylPhotoinduced Linkage Isomerizationhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The ambidentate nitrite ion, NO2−, is a biologically relevant species that can be coordinated to transition metals via the nitrogen or oxygen atom. Most of its physiological effects involve metalloproteins so it is important to understand the factors that control the predominance of one or another isomer. In this work, we present the syntheses and characterization by spectroscopy, electrochemistry and DFT calculations of new rhenium(I) tricarbonyl complexes with different polypyridyl ligands in the coordination sphere and with the nitrite ion coordinated through either its N- or O-atom. For two of them we have determined their crystal structures by X-ray diffraction and we have found that in the solid when the ancilliary ligand is bpy the N-binding mode is the most stable, while dmb is the ligand, the –CH3 substituents imposed the C–H (methyl group)⋯O–NO (nitrito) interactions favoring the O-binding mode. However, at room temperature in CH2Cl2 the nitro isomer is the most stable for both complexes in agreement with DFT calculations. Both complexes exhibit photoinduced linkage isomerism which could be of interesting in the design of new materials. Although nitro complexes are precursors of nitrosyl compounds, in this work the synthesis of the nitrosyl complexes as solid could not be possible because there is higher π-backbonding from Re(I) to the carbonyl groups, or to the polypyridil ligands instead of to the NO group, which is π-acceptor, in consequence the nitrosyl complexes are unstable and decompose immediately to the solvate complexes.Fil: Domínguez, Sofía Eugenia. 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: Alborés, Pablo. 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: 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; ArgentinaElsevier2013-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/30209Domínguez, Sofía Eugenia; Alborés, Pablo; Fagalde, Florencia; Photoinduced linkage isomerization in new rhenium(I) tricarbonyl complexes coordinated to N-nitrite and O-nitrite; Elsevier; Polyhedron; 67; 10-2013; 471-4800277-5387CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.poly.2013.10.002info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0277538713006943info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:29:56Zoai:ri.conicet.gov.ar:11336/30209instacron: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 10:29:56.385CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Photoinduced linkage isomerization in new rhenium(I) tricarbonyl complexes coordinated to N-nitrite and O-nitrite
title Photoinduced linkage isomerization in new rhenium(I) tricarbonyl complexes coordinated to N-nitrite and O-nitrite
spellingShingle Photoinduced linkage isomerization in new rhenium(I) tricarbonyl complexes coordinated to N-nitrite and O-nitrite
Domínguez, Sofía Eugenia
Nitro
Nitrito
Rhenium (I) Tricarbonyl
Photoinduced Linkage Isomerization
title_short Photoinduced linkage isomerization in new rhenium(I) tricarbonyl complexes coordinated to N-nitrite and O-nitrite
title_full Photoinduced linkage isomerization in new rhenium(I) tricarbonyl complexes coordinated to N-nitrite and O-nitrite
title_fullStr Photoinduced linkage isomerization in new rhenium(I) tricarbonyl complexes coordinated to N-nitrite and O-nitrite
title_full_unstemmed Photoinduced linkage isomerization in new rhenium(I) tricarbonyl complexes coordinated to N-nitrite and O-nitrite
title_sort Photoinduced linkage isomerization in new rhenium(I) tricarbonyl complexes coordinated to N-nitrite and O-nitrite
dc.creator.none.fl_str_mv Domínguez, Sofía Eugenia
Alborés, Pablo
Fagalde, Florencia
author Domínguez, Sofía Eugenia
author_facet Domínguez, Sofía Eugenia
Alborés, Pablo
Fagalde, Florencia
author_role author
author2 Alborés, Pablo
Fagalde, Florencia
author2_role author
author
dc.subject.none.fl_str_mv Nitro
Nitrito
Rhenium (I) Tricarbonyl
Photoinduced Linkage Isomerization
topic Nitro
Nitrito
Rhenium (I) Tricarbonyl
Photoinduced Linkage Isomerization
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The ambidentate nitrite ion, NO2−, is a biologically relevant species that can be coordinated to transition metals via the nitrogen or oxygen atom. Most of its physiological effects involve metalloproteins so it is important to understand the factors that control the predominance of one or another isomer. In this work, we present the syntheses and characterization by spectroscopy, electrochemistry and DFT calculations of new rhenium(I) tricarbonyl complexes with different polypyridyl ligands in the coordination sphere and with the nitrite ion coordinated through either its N- or O-atom. For two of them we have determined their crystal structures by X-ray diffraction and we have found that in the solid when the ancilliary ligand is bpy the N-binding mode is the most stable, while dmb is the ligand, the –CH3 substituents imposed the C–H (methyl group)⋯O–NO (nitrito) interactions favoring the O-binding mode. However, at room temperature in CH2Cl2 the nitro isomer is the most stable for both complexes in agreement with DFT calculations. Both complexes exhibit photoinduced linkage isomerism which could be of interesting in the design of new materials. Although nitro complexes are precursors of nitrosyl compounds, in this work the synthesis of the nitrosyl complexes as solid could not be possible because there is higher π-backbonding from Re(I) to the carbonyl groups, or to the polypyridil ligands instead of to the NO group, which is π-acceptor, in consequence the nitrosyl complexes are unstable and decompose immediately to the solvate complexes.
Fil: Domínguez, Sofía Eugenia. 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: Alborés, Pablo. 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: 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
description The ambidentate nitrite ion, NO2−, is a biologically relevant species that can be coordinated to transition metals via the nitrogen or oxygen atom. Most of its physiological effects involve metalloproteins so it is important to understand the factors that control the predominance of one or another isomer. In this work, we present the syntheses and characterization by spectroscopy, electrochemistry and DFT calculations of new rhenium(I) tricarbonyl complexes with different polypyridyl ligands in the coordination sphere and with the nitrite ion coordinated through either its N- or O-atom. For two of them we have determined their crystal structures by X-ray diffraction and we have found that in the solid when the ancilliary ligand is bpy the N-binding mode is the most stable, while dmb is the ligand, the –CH3 substituents imposed the C–H (methyl group)⋯O–NO (nitrito) interactions favoring the O-binding mode. However, at room temperature in CH2Cl2 the nitro isomer is the most stable for both complexes in agreement with DFT calculations. Both complexes exhibit photoinduced linkage isomerism which could be of interesting in the design of new materials. Although nitro complexes are precursors of nitrosyl compounds, in this work the synthesis of the nitrosyl complexes as solid could not be possible because there is higher π-backbonding from Re(I) to the carbonyl groups, or to the polypyridil ligands instead of to the NO group, which is π-acceptor, in consequence the nitrosyl complexes are unstable and decompose immediately to the solvate complexes.
publishDate 2013
dc.date.none.fl_str_mv 2013-10
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/11336/30209
Domínguez, Sofía Eugenia; Alborés, Pablo; Fagalde, Florencia; Photoinduced linkage isomerization in new rhenium(I) tricarbonyl complexes coordinated to N-nitrite and O-nitrite; Elsevier; Polyhedron; 67; 10-2013; 471-480
0277-5387
CONICET Digital
CONICET
url http://hdl.handle.net/11336/30209
identifier_str_mv Domínguez, Sofía Eugenia; Alborés, Pablo; Fagalde, Florencia; Photoinduced linkage isomerization in new rhenium(I) tricarbonyl complexes coordinated to N-nitrite and O-nitrite; Elsevier; Polyhedron; 67; 10-2013; 471-480
0277-5387
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.poly.2013.10.002
info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0277538713006943
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
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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