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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/104277
Ver los metadatos del registro completo
id |
CONICETDig_5c2f147b0287c0938469fb53296e30b1 |
---|---|
oai_identifier_str |
oai:ri.conicet.gov.ar:11336/104277 |
network_acronym_str |
CONICETDig |
repository_id_str |
3498 |
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/ |
dc.format.none.fl_str_mv |
application/pdf application/pdf application/pdf application/pdf |
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) |
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 |
_version_ |
1844613318426230784 |
score |
13.070432 |