Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity

Autores
Peyrot, Analía Mercedes; Zelaya, María Priscila; Alborés, Pablo; Fagalde, Florencia
Año de publicación
2023
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In this work, we report the synthesis and physicochemical characterization of new chloro and aqua mononuclear Ru (II) complexes of formula [Ru(LLL)(dpp)Cl]PF6 and [Ru(LLL)(dpp)OH2](PF6)2 (LLL=tpy =2,2’ : 6’,2’’-terpyridine; tptz=2,4,6-tris(2-pyridyl)-1,3,5-triazine and dpp=2,3-bis(2-pyridil)pyrazine). For the complex [Ru(tptz)(dpp)Cl]PF6, the complete structure was determined by X-ray diffraction. Catalytic studies of aqua-complexes revealed that they are active for the water oxidation reaction at pH 1 using cerium ammonium nitrate (CAN) as a sacrificial oxidant. Also, we were able to establish the reaction mechanism and rate constants of each stage of the catalytic cycle, turnover frequencies (TOFs), and turnover numberes (TONs). The experimental TON values for the aqua complexes were very close to the theoretical value of 7.5, indicating a high degree of recovery. DFT and TD-DFT calculations of electronic states for all complexes were consistent with experimental results and allowed the complete assignment of their UV-Visible bands and redox states.
Fil: Peyrot, Analía 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: Zelaya, María Priscila. Universidad Nacional de Tucumán. Instituto de Física del Noroeste Argentino. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet Noa Sur. Instituto de Física del Noroeste Argentino; 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
2,3-BIS(2-PYRIDYL)PYRAZINE
AQUO MONONUCLEAR RU(II) COMPLEXES
DFT AND TD-DFT CALCULATIONS
RUTHENIUM(II) COMPLEXES
WATER OXIDATION
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:11336/227892
Acceder
id CONICETDig_663dc54c7f510e0adc591793f0d36883
oai_identifier_str oai:ri.conicet.gov.ar:11336/227892
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic ActivityPeyrot, Analía MercedesZelaya, María PriscilaAlborés, PabloFagalde, Florencia2,3-BIS(2-PYRIDYL)PYRAZINEAQUO MONONUCLEAR RU(II) COMPLEXESDFT AND TD-DFT CALCULATIONSRUTHENIUM(II) COMPLEXESWATER OXIDATIONhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In this work, we report the synthesis and physicochemical characterization of new chloro and aqua mononuclear Ru (II) complexes of formula [Ru(LLL)(dpp)Cl]PF6 and [Ru(LLL)(dpp)OH2](PF6)2 (LLL=tpy =2,2’ : 6’,2’’-terpyridine; tptz=2,4,6-tris(2-pyridyl)-1,3,5-triazine and dpp=2,3-bis(2-pyridil)pyrazine). For the complex [Ru(tptz)(dpp)Cl]PF6, the complete structure was determined by X-ray diffraction. Catalytic studies of aqua-complexes revealed that they are active for the water oxidation reaction at pH 1 using cerium ammonium nitrate (CAN) as a sacrificial oxidant. Also, we were able to establish the reaction mechanism and rate constants of each stage of the catalytic cycle, turnover frequencies (TOFs), and turnover numberes (TONs). The experimental TON values for the aqua complexes were very close to the theoretical value of 7.5, indicating a high degree of recovery. DFT and TD-DFT calculations of electronic states for all complexes were consistent with experimental results and allowed the complete assignment of their UV-Visible bands and redox states.Fil: Peyrot, Analía 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: Zelaya, María Priscila. Universidad Nacional de Tucumán. Instituto de Física del Noroeste Argentino. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet Noa Sur. Instituto de Física del Noroeste Argentino; 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; ArgentinaWiley VCH Verlag2023-03info: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/11336/227892Peyrot, Analía Mercedes; Zelaya, María Priscila; Alborés, Pablo; Fagalde, Florencia; Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity; Wiley VCH Verlag; European Journal of Inorganic Chemistry; 26; 16; 3-2023; 1-371434-1948CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/10.1002/ejic.202300021info:eu-repo/semantics/altIdentifier/doi/10.1002/ejic.202300021info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:14:25Zoai:ri.conicet.gov.ar:11336/227892instacron: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 10:14:25.912CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity
title Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity
spellingShingle Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity
Peyrot, Analía Mercedes
2,3-BIS(2-PYRIDYL)PYRAZINE
AQUO MONONUCLEAR RU(II) COMPLEXES
DFT AND TD-DFT CALCULATIONS
RUTHENIUM(II) COMPLEXES
WATER OXIDATION
title_short Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity
title_full Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity
title_fullStr Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity
title_full_unstemmed Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity
title_sort Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity
dc.creator.none.fl_str_mv Peyrot, Analía Mercedes
Zelaya, María Priscila
Alborés, Pablo
Fagalde, Florencia
author Peyrot, Analía Mercedes
author_facet Peyrot, Analía Mercedes
Zelaya, María Priscila
Alborés, Pablo
Fagalde, Florencia
author_role author
author2 Zelaya, María Priscila
Alborés, Pablo
Fagalde, Florencia
author2_role author
author
author
dc.subject.none.fl_str_mv 2,3-BIS(2-PYRIDYL)PYRAZINE
AQUO MONONUCLEAR RU(II) COMPLEXES
DFT AND TD-DFT CALCULATIONS
RUTHENIUM(II) COMPLEXES
WATER OXIDATION
topic 2,3-BIS(2-PYRIDYL)PYRAZINE
AQUO MONONUCLEAR RU(II) COMPLEXES
DFT AND TD-DFT CALCULATIONS
RUTHENIUM(II) COMPLEXES
WATER OXIDATION
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In this work, we report the synthesis and physicochemical characterization of new chloro and aqua mononuclear Ru (II) complexes of formula [Ru(LLL)(dpp)Cl]PF6 and [Ru(LLL)(dpp)OH2](PF6)2 (LLL=tpy =2,2’ : 6’,2’’-terpyridine; tptz=2,4,6-tris(2-pyridyl)-1,3,5-triazine and dpp=2,3-bis(2-pyridil)pyrazine). For the complex [Ru(tptz)(dpp)Cl]PF6, the complete structure was determined by X-ray diffraction. Catalytic studies of aqua-complexes revealed that they are active for the water oxidation reaction at pH 1 using cerium ammonium nitrate (CAN) as a sacrificial oxidant. Also, we were able to establish the reaction mechanism and rate constants of each stage of the catalytic cycle, turnover frequencies (TOFs), and turnover numberes (TONs). The experimental TON values for the aqua complexes were very close to the theoretical value of 7.5, indicating a high degree of recovery. DFT and TD-DFT calculations of electronic states for all complexes were consistent with experimental results and allowed the complete assignment of their UV-Visible bands and redox states.
Fil: Peyrot, Analía 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: Zelaya, María Priscila. Universidad Nacional de Tucumán. Instituto de Física del Noroeste Argentino. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet Noa Sur. Instituto de Física del Noroeste Argentino; 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 In this work, we report the synthesis and physicochemical characterization of new chloro and aqua mononuclear Ru (II) complexes of formula [Ru(LLL)(dpp)Cl]PF6 and [Ru(LLL)(dpp)OH2](PF6)2 (LLL=tpy =2,2’ : 6’,2’’-terpyridine; tptz=2,4,6-tris(2-pyridyl)-1,3,5-triazine and dpp=2,3-bis(2-pyridil)pyrazine). For the complex [Ru(tptz)(dpp)Cl]PF6, the complete structure was determined by X-ray diffraction. Catalytic studies of aqua-complexes revealed that they are active for the water oxidation reaction at pH 1 using cerium ammonium nitrate (CAN) as a sacrificial oxidant. Also, we were able to establish the reaction mechanism and rate constants of each stage of the catalytic cycle, turnover frequencies (TOFs), and turnover numberes (TONs). The experimental TON values for the aqua complexes were very close to the theoretical value of 7.5, indicating a high degree of recovery. DFT and TD-DFT calculations of electronic states for all complexes were consistent with experimental results and allowed the complete assignment of their UV-Visible bands and redox states.
publishDate 2023
dc.date.none.fl_str_mv 2023-03
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/11336/227892
Peyrot, Analía Mercedes; Zelaya, María Priscila; Alborés, Pablo; Fagalde, Florencia; Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity; Wiley VCH Verlag; European Journal of Inorganic Chemistry; 26; 16; 3-2023; 1-37
1434-1948
CONICET Digital
CONICET
url http://hdl.handle.net/11336/227892
identifier_str_mv Peyrot, Analía Mercedes; Zelaya, María Priscila; Alborés, Pablo; Fagalde, Florencia; Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity; Wiley VCH Verlag; European Journal of Inorganic Chemistry; 26; 16; 3-2023; 1-37
1434-1948
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://onlinelibrary.wiley.com/doi/10.1002/ejic.202300021
info:eu-repo/semantics/altIdentifier/doi/10.1002/ejic.202300021
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 Wiley VCH Verlag
publisher.none.fl_str_mv Wiley VCH Verlag
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_ 1844614071713792000
score 13.070432

Publicaciones similares