Synthesis and structure of novel RuII-N≡C-Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effects

Autores
Mola, Joaquim; Pujol, David; Rodríguez, Montserrat; Romero, Isabel; Sala, Xavier; Katz, Néstor Eduardo; Parella, Teodor; Benet Buchholz, Jordi; Fontrodona, Xavier; Llobet, Antoni
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The synthesis and isolation of new RuIIacetonitrile complexes, of general formula trans,fac-[Ru(bpea)(B)(MeCN)](BF4)2 (bpea = N,N-bis(2-pyridylmethyl)ethylamine; B = bpy, 2,2′-bipyridine, 4; B = dppe, 1,2-bis(diphenylphosphino)ethane, 5), together with a synthetic intermediate trans,fac-[Ru(NO3)(bpea)(dppe)](BF4), 6, are described. Ru(bpea)Cl3, 1, is used as the starting material for the synthesis of all complexes 2-6 presented in this paper, which are characterized by analytical, spectroscopic (IR, UV/Vis, 1D and 2D NMR), and electrochemical techniques (cyclic voltammetry). Furthermore, complexes 4, 5, and 6 have also been characterized in the solid state by single crystal X-ray diffraction analysis. Their structures show a distorted octahedral geometry where the bpea ligand binds in a facial mode, the bidentate ligands bpy and dppe bind in a chelate manner, and finally the MeCN or the NO3 - ligand occupy the sixth position of the octahedral Ru metal centre. The kinetics of the basic hydrolysis of the coordinated MeCN ligand for complexes 4 and 5 and for the related complex [Ru(phen)(MeCN)([9]aneS3)](BF4) 2, 7, which contains the 1,4,7-trithiacyclonane ligand ([9]aneS 3) and 1,10-phenanthroline (phen) is also described. Second-order rate constants for acetonitrile hydrolysis measured at 25°C of k = 1.01 10-3 M-1 s-1 for 4, 1.08 10-4 M -1 s-1 for 5, and 6.8 10-3 M-1 s-1 for 7, have been obtained through UV-vis spectroscopy. Activation parameters have also been determined over the temperature range 25.0-45.0°C and agree with a mechanism that involves an associative rate-determining step. Finally the electronic and steric influence of the auxiliary ligands on this reaction for the above and related complexes is discussed.
Fil: Mola, Joaquim. Universidad de Girona; España
Fil: Pujol, David. Universidad de Girona; España
Fil: Rodríguez, Montserrat. Universidad de Girona; España
Fil: Romero, Isabel. Universidad de Girona; España
Fil: Sala, Xavier. Institut Català d'Investigació Química; España
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. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; Argentina
Fil: Parella, Teodor. Universitat Autònoma de Barcelona; España
Fil: Benet Buchholz, Jordi. Institut Català d'Investigació Química; España
Fil: Fontrodona, Xavier. Universidad de Girona; España
Fil: Llobet, Antoni. Institut Català d'Investigació Química; España
Materia
Ruthenium
Hydrolysis
Spectroscopy
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:11336/54674
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/54674
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Synthesis and structure of novel RuII-N≡C-Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effectsMola, JoaquimPujol, DavidRodríguez, MontserratRomero, IsabelSala, XavierKatz, Néstor EduardoParella, TeodorBenet Buchholz, JordiFontrodona, XavierLlobet, AntoniRutheniumHydrolysisSpectroscopyhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The synthesis and isolation of new RuIIacetonitrile complexes, of general formula trans,fac-[Ru(bpea)(B)(MeCN)](BF4)2 (bpea = N,N-bis(2-pyridylmethyl)ethylamine; B = bpy, 2,2′-bipyridine, 4; B = dppe, 1,2-bis(diphenylphosphino)ethane, 5), together with a synthetic intermediate trans,fac-[Ru(NO3)(bpea)(dppe)](BF4), 6, are described. Ru(bpea)Cl3, 1, is used as the starting material for the synthesis of all complexes 2-6 presented in this paper, which are characterized by analytical, spectroscopic (IR, UV/Vis, 1D and 2D NMR), and electrochemical techniques (cyclic voltammetry). Furthermore, complexes 4, 5, and 6 have also been characterized in the solid state by single crystal X-ray diffraction analysis. Their structures show a distorted octahedral geometry where the bpea ligand binds in a facial mode, the bidentate ligands bpy and dppe bind in a chelate manner, and finally the MeCN or the NO3 - ligand occupy the sixth position of the octahedral Ru metal centre. The kinetics of the basic hydrolysis of the coordinated MeCN ligand for complexes 4 and 5 and for the related complex [Ru(phen)(MeCN)([9]aneS3)](BF4) 2, 7, which contains the 1,4,7-trithiacyclonane ligand ([9]aneS 3) and 1,10-phenanthroline (phen) is also described. Second-order rate constants for acetonitrile hydrolysis measured at 25°C of k = 1.01 10-3 M-1 s-1 for 4, 1.08 10-4 M -1 s-1 for 5, and 6.8 10-3 M-1 s-1 for 7, have been obtained through UV-vis spectroscopy. Activation parameters have also been determined over the temperature range 25.0-45.0°C and agree with a mechanism that involves an associative rate-determining step. Finally the electronic and steric influence of the auxiliary ligands on this reaction for the above and related complexes is discussed.Fil: Mola, Joaquim. Universidad de Girona; EspañaFil: Pujol, David. Universidad de Girona; EspañaFil: Rodríguez, Montserrat. Universidad de Girona; EspañaFil: Romero, Isabel. Universidad de Girona; EspañaFil: Sala, Xavier. Institut Català d'Investigació Química; EspañaFil: 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. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; ArgentinaFil: Parella, Teodor. Universitat Autònoma de Barcelona; EspañaFil: Benet Buchholz, Jordi. Institut Català d'Investigació Química; EspañaFil: Fontrodona, Xavier. Universidad de Girona; EspañaFil: Llobet, Antoni. Institut Català d'Investigació Química; EspañaCsiro Publishing2009-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/54674Mola, Joaquim; Pujol, David; Rodríguez, Montserrat; Romero, Isabel; Sala, Xavier; et al.; Synthesis and structure of novel RuII-N≡C-Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effects; Csiro Publishing; Australian Journal of Chemistry; 62; 12; 9-2009; 1675-16830004-9425CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://www.publish.csiro.au/CH/CH08563info:eu-repo/semantics/altIdentifier/doi/10.1071/CH08563info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:12:48Zoai:ri.conicet.gov.ar:11336/54674instacron: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 10:12:48.904CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Synthesis and structure of novel RuII-N≡C-Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effects
title Synthesis and structure of novel RuII-N≡C-Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effects
spellingShingle Synthesis and structure of novel RuII-N≡C-Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effects
Mola, Joaquim
Ruthenium
Hydrolysis
Spectroscopy
title_short Synthesis and structure of novel RuII-N≡C-Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effects
title_full Synthesis and structure of novel RuII-N≡C-Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effects
title_fullStr Synthesis and structure of novel RuII-N≡C-Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effects
title_full_unstemmed Synthesis and structure of novel RuII-N≡C-Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effects
title_sort Synthesis and structure of novel RuII-N≡C-Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effects
dc.creator.none.fl_str_mv Mola, Joaquim
Pujol, David
Rodríguez, Montserrat
Romero, Isabel
Sala, Xavier
Katz, Néstor Eduardo
Parella, Teodor
Benet Buchholz, Jordi
Fontrodona, Xavier
Llobet, Antoni
author Mola, Joaquim
author_facet Mola, Joaquim
Pujol, David
Rodríguez, Montserrat
Romero, Isabel
Sala, Xavier
Katz, Néstor Eduardo
Parella, Teodor
Benet Buchholz, Jordi
Fontrodona, Xavier
Llobet, Antoni
author_role author
author2 Pujol, David
Rodríguez, Montserrat
Romero, Isabel
Sala, Xavier
Katz, Néstor Eduardo
Parella, Teodor
Benet Buchholz, Jordi
Fontrodona, Xavier
Llobet, Antoni
author2_role author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Ruthenium
Hydrolysis
Spectroscopy
topic Ruthenium
Hydrolysis
Spectroscopy
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 synthesis and isolation of new RuIIacetonitrile complexes, of general formula trans,fac-[Ru(bpea)(B)(MeCN)](BF4)2 (bpea = N,N-bis(2-pyridylmethyl)ethylamine; B = bpy, 2,2′-bipyridine, 4; B = dppe, 1,2-bis(diphenylphosphino)ethane, 5), together with a synthetic intermediate trans,fac-[Ru(NO3)(bpea)(dppe)](BF4), 6, are described. Ru(bpea)Cl3, 1, is used as the starting material for the synthesis of all complexes 2-6 presented in this paper, which are characterized by analytical, spectroscopic (IR, UV/Vis, 1D and 2D NMR), and electrochemical techniques (cyclic voltammetry). Furthermore, complexes 4, 5, and 6 have also been characterized in the solid state by single crystal X-ray diffraction analysis. Their structures show a distorted octahedral geometry where the bpea ligand binds in a facial mode, the bidentate ligands bpy and dppe bind in a chelate manner, and finally the MeCN or the NO3 - ligand occupy the sixth position of the octahedral Ru metal centre. The kinetics of the basic hydrolysis of the coordinated MeCN ligand for complexes 4 and 5 and for the related complex [Ru(phen)(MeCN)([9]aneS3)](BF4) 2, 7, which contains the 1,4,7-trithiacyclonane ligand ([9]aneS 3) and 1,10-phenanthroline (phen) is also described. Second-order rate constants for acetonitrile hydrolysis measured at 25°C of k = 1.01 10-3 M-1 s-1 for 4, 1.08 10-4 M -1 s-1 for 5, and 6.8 10-3 M-1 s-1 for 7, have been obtained through UV-vis spectroscopy. Activation parameters have also been determined over the temperature range 25.0-45.0°C and agree with a mechanism that involves an associative rate-determining step. Finally the electronic and steric influence of the auxiliary ligands on this reaction for the above and related complexes is discussed.
Fil: Mola, Joaquim. Universidad de Girona; España
Fil: Pujol, David. Universidad de Girona; España
Fil: Rodríguez, Montserrat. Universidad de Girona; España
Fil: Romero, Isabel. Universidad de Girona; España
Fil: Sala, Xavier. Institut Català d'Investigació Química; España
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. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; Argentina
Fil: Parella, Teodor. Universitat Autònoma de Barcelona; España
Fil: Benet Buchholz, Jordi. Institut Català d'Investigació Química; España
Fil: Fontrodona, Xavier. Universidad de Girona; España
Fil: Llobet, Antoni. Institut Català d'Investigació Química; España
description The synthesis and isolation of new RuIIacetonitrile complexes, of general formula trans,fac-[Ru(bpea)(B)(MeCN)](BF4)2 (bpea = N,N-bis(2-pyridylmethyl)ethylamine; B = bpy, 2,2′-bipyridine, 4; B = dppe, 1,2-bis(diphenylphosphino)ethane, 5), together with a synthetic intermediate trans,fac-[Ru(NO3)(bpea)(dppe)](BF4), 6, are described. Ru(bpea)Cl3, 1, is used as the starting material for the synthesis of all complexes 2-6 presented in this paper, which are characterized by analytical, spectroscopic (IR, UV/Vis, 1D and 2D NMR), and electrochemical techniques (cyclic voltammetry). Furthermore, complexes 4, 5, and 6 have also been characterized in the solid state by single crystal X-ray diffraction analysis. Their structures show a distorted octahedral geometry where the bpea ligand binds in a facial mode, the bidentate ligands bpy and dppe bind in a chelate manner, and finally the MeCN or the NO3 - ligand occupy the sixth position of the octahedral Ru metal centre. The kinetics of the basic hydrolysis of the coordinated MeCN ligand for complexes 4 and 5 and for the related complex [Ru(phen)(MeCN)([9]aneS3)](BF4) 2, 7, which contains the 1,4,7-trithiacyclonane ligand ([9]aneS 3) and 1,10-phenanthroline (phen) is also described. Second-order rate constants for acetonitrile hydrolysis measured at 25°C of k = 1.01 10-3 M-1 s-1 for 4, 1.08 10-4 M -1 s-1 for 5, and 6.8 10-3 M-1 s-1 for 7, have been obtained through UV-vis spectroscopy. Activation parameters have also been determined over the temperature range 25.0-45.0°C and agree with a mechanism that involves an associative rate-determining step. Finally the electronic and steric influence of the auxiliary ligands on this reaction for the above and related complexes is discussed.
publishDate 2009
dc.date.none.fl_str_mv 2009-09
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/11336/54674
Mola, Joaquim; Pujol, David; Rodríguez, Montserrat; Romero, Isabel; Sala, Xavier; et al.; Synthesis and structure of novel RuII-N≡C-Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effects; Csiro Publishing; Australian Journal of Chemistry; 62; 12; 9-2009; 1675-1683
0004-9425
CONICET Digital
CONICET
url http://hdl.handle.net/11336/54674
identifier_str_mv Mola, Joaquim; Pujol, David; Rodríguez, Montserrat; Romero, Isabel; Sala, Xavier; et al.; Synthesis and structure of novel RuII-N≡C-Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effects; Csiro Publishing; Australian Journal of Chemistry; 62; 12; 9-2009; 1675-1683
0004-9425
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://www.publish.csiro.au/CH/CH08563
info:eu-repo/semantics/altIdentifier/doi/10.1071/CH08563
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 Csiro Publishing
publisher.none.fl_str_mv Csiro Publishing
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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score 13.070432

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