A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study

Autores
de Candia, Ariel Gustavo; Marcolongo, Juan Pablo; Slep, Leonardo Daniel
Año de publicación
2007
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The complex cis-[Ru(L-py)NO](3+) (I) (L-py = N-(2-methylpyridyl) 1,4,8,11-tetraazacyclotetradecane) was prepared by the stoichiometric reaction between Ru(dmso)(4)Cl-2 and L-py and an excess of NaNO2 in ethanolic medium, followed by acidification of the solution. The diamagnetic species was isolated as its hexafluorophosphate salt, and fully characterized by IR (nu(NO) = 1917 cm(-1)) and diverse NMR techniques in combination with theoretical computations based on the density functional theory (DFT). The compound displays strong electronic transitions below 300 nm and weak ones in the visible region of the spectrum, all of them solvent insensitive. The reaction of cis-[Ru(L-py)NO](3+) with OH- generates the strongly colored nitro compound cis-[Ru(L-py)NO2](+) (II) The {RuNO}(6) compound can be interconverted into the one-electron reduced {RuNO}(7) species cis-[Ru(L-py)NO](2+) (III). The reduction process is completely reversible in the cyclic voltammetry timescale with E-0 (versus Ag/AgCl, 3 M Cl-) = -0.02 V and 0.18 V in water and acetonitrile, respectively. Controlled potential reduction in both solvents yields to the quantitative formation of 111, a process which involves significant changes in the electronic spectroscopy. The {RuNO}(7) Species proved to be inert against ligand loss, and electrogenerated solutions remained unchanged for several hours if protected from atmospheric oxygen. Electrochemical reoxidation or exposure to air lead to the complete recovery of the starting cis-[Ru(L-py)NO](3+) material, without signs of secondary reactions. The robustness of the coordination sphere appears as a consequence of the multidentate nature of L-py. (c) 2007 Elsevier Ltd. All rights reserved.
Fil: de Candia, Ariel Gustavo. 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: Marcolongo, Juan 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: 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 Chemistry
NMR
Macrocycles
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:11336/104277

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network_name_str CONICET Digital (CONICET)
spelling A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical studyde Candia, Ariel GustavoMarcolongo, Juan PabloSlep, Leonardo DanielNitrosyl ChemistryNMRMacrocycleshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The complex cis-[Ru(L-py)NO](3+) (I) (L-py = N-(2-methylpyridyl) 1,4,8,11-tetraazacyclotetradecane) was prepared by the stoichiometric reaction between Ru(dmso)(4)Cl-2 and L-py and an excess of NaNO2 in ethanolic medium, followed by acidification of the solution. The diamagnetic species was isolated as its hexafluorophosphate salt, and fully characterized by IR (nu(NO) = 1917 cm(-1)) and diverse NMR techniques in combination with theoretical computations based on the density functional theory (DFT). The compound displays strong electronic transitions below 300 nm and weak ones in the visible region of the spectrum, all of them solvent insensitive. The reaction of cis-[Ru(L-py)NO](3+) with OH- generates the strongly colored nitro compound cis-[Ru(L-py)NO2](+) (II) The {RuNO}(6) compound can be interconverted into the one-electron reduced {RuNO}(7) species cis-[Ru(L-py)NO](2+) (III). The reduction process is completely reversible in the cyclic voltammetry timescale with E-0 (versus Ag/AgCl, 3 M Cl-) = -0.02 V and 0.18 V in water and acetonitrile, respectively. Controlled potential reduction in both solvents yields to the quantitative formation of 111, a process which involves significant changes in the electronic spectroscopy. The {RuNO}(7) Species proved to be inert against ligand loss, and electrogenerated solutions remained unchanged for several hours if protected from atmospheric oxygen. Electrochemical reoxidation or exposure to air lead to the complete recovery of the starting cis-[Ru(L-py)NO](3+) material, without signs of secondary reactions. The robustness of the coordination sphere appears as a consequence of the multidentate nature of L-py. (c) 2007 Elsevier Ltd. All rights reserved.Fil: de Candia, Ariel Gustavo. 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: Marcolongo, Juan 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: 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; ArgentinaPergamon-Elsevier Science Ltd2007-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/104277de Candia, Ariel Gustavo; Marcolongo, Juan Pablo; Slep, Leonardo Daniel; A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study; Pergamon-Elsevier Science Ltd; Polyhedron; 26; 16; 10-2007; 4719-47300277-5387CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S027753870700277Xinfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.poly.2007.04.038info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:41:47Zoai:ri.conicet.gov.ar:11336/104277instacron: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 09:41:48.053CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study
title A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study
spellingShingle A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study
de Candia, Ariel Gustavo
Nitrosyl Chemistry
NMR
Macrocycles
title_short A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study
title_full A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study
title_fullStr A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study
title_full_unstemmed A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study
title_sort A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study
dc.creator.none.fl_str_mv de Candia, Ariel Gustavo
Marcolongo, Juan Pablo
Slep, Leonardo Daniel
author de Candia, Ariel Gustavo
author_facet de Candia, Ariel Gustavo
Marcolongo, Juan Pablo
Slep, Leonardo Daniel
author_role author
author2 Marcolongo, Juan Pablo
Slep, Leonardo Daniel
author2_role author
author
dc.subject.none.fl_str_mv Nitrosyl Chemistry
NMR
Macrocycles
topic Nitrosyl Chemistry
NMR
Macrocycles
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 complex cis-[Ru(L-py)NO](3+) (I) (L-py = N-(2-methylpyridyl) 1,4,8,11-tetraazacyclotetradecane) was prepared by the stoichiometric reaction between Ru(dmso)(4)Cl-2 and L-py and an excess of NaNO2 in ethanolic medium, followed by acidification of the solution. The diamagnetic species was isolated as its hexafluorophosphate salt, and fully characterized by IR (nu(NO) = 1917 cm(-1)) and diverse NMR techniques in combination with theoretical computations based on the density functional theory (DFT). The compound displays strong electronic transitions below 300 nm and weak ones in the visible region of the spectrum, all of them solvent insensitive. The reaction of cis-[Ru(L-py)NO](3+) with OH- generates the strongly colored nitro compound cis-[Ru(L-py)NO2](+) (II) The {RuNO}(6) compound can be interconverted into the one-electron reduced {RuNO}(7) species cis-[Ru(L-py)NO](2+) (III). The reduction process is completely reversible in the cyclic voltammetry timescale with E-0 (versus Ag/AgCl, 3 M Cl-) = -0.02 V and 0.18 V in water and acetonitrile, respectively. Controlled potential reduction in both solvents yields to the quantitative formation of 111, a process which involves significant changes in the electronic spectroscopy. The {RuNO}(7) Species proved to be inert against ligand loss, and electrogenerated solutions remained unchanged for several hours if protected from atmospheric oxygen. Electrochemical reoxidation or exposure to air lead to the complete recovery of the starting cis-[Ru(L-py)NO](3+) material, without signs of secondary reactions. The robustness of the coordination sphere appears as a consequence of the multidentate nature of L-py. (c) 2007 Elsevier Ltd. All rights reserved.
Fil: de Candia, Ariel Gustavo. 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: Marcolongo, Juan 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: 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 The complex cis-[Ru(L-py)NO](3+) (I) (L-py = N-(2-methylpyridyl) 1,4,8,11-tetraazacyclotetradecane) was prepared by the stoichiometric reaction between Ru(dmso)(4)Cl-2 and L-py and an excess of NaNO2 in ethanolic medium, followed by acidification of the solution. The diamagnetic species was isolated as its hexafluorophosphate salt, and fully characterized by IR (nu(NO) = 1917 cm(-1)) and diverse NMR techniques in combination with theoretical computations based on the density functional theory (DFT). The compound displays strong electronic transitions below 300 nm and weak ones in the visible region of the spectrum, all of them solvent insensitive. The reaction of cis-[Ru(L-py)NO](3+) with OH- generates the strongly colored nitro compound cis-[Ru(L-py)NO2](+) (II) The {RuNO}(6) compound can be interconverted into the one-electron reduced {RuNO}(7) species cis-[Ru(L-py)NO](2+) (III). The reduction process is completely reversible in the cyclic voltammetry timescale with E-0 (versus Ag/AgCl, 3 M Cl-) = -0.02 V and 0.18 V in water and acetonitrile, respectively. Controlled potential reduction in both solvents yields to the quantitative formation of 111, a process which involves significant changes in the electronic spectroscopy. The {RuNO}(7) Species proved to be inert against ligand loss, and electrogenerated solutions remained unchanged for several hours if protected from atmospheric oxygen. Electrochemical reoxidation or exposure to air lead to the complete recovery of the starting cis-[Ru(L-py)NO](3+) material, without signs of secondary reactions. The robustness of the coordination sphere appears as a consequence of the multidentate nature of L-py. (c) 2007 Elsevier Ltd. All rights reserved.
publishDate 2007
dc.date.none.fl_str_mv 2007-10
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/11336/104277
de Candia, Ariel Gustavo; Marcolongo, Juan Pablo; Slep, Leonardo Daniel; A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study; Pergamon-Elsevier Science Ltd; Polyhedron; 26; 16; 10-2007; 4719-4730
0277-5387
CONICET Digital
CONICET
url http://hdl.handle.net/11336/104277
identifier_str_mv de Candia, Ariel Gustavo; Marcolongo, Juan Pablo; Slep, Leonardo Daniel; A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study; Pergamon-Elsevier Science Ltd; Polyhedron; 26; 16; 10-2007; 4719-4730
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/url/https://www.sciencedirect.com/science/article/abs/pii/S027753870700277X
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.poly.2007.04.038
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/
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application/pdf
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dc.publisher.none.fl_str_mv Pergamon-Elsevier Science Ltd
publisher.none.fl_str_mv Pergamon-Elsevier Science Ltd
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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