Kinetics of the homogeneous hydrogenation of avermectins catalyzed by RhCl(Ph3P)3 complexes

Autores
Zgolicz, Patricia Daniela; Cabrera, Maria Ines; Grau, Ricardo José Antonio
Año de publicación
2005
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The kinetics of the hydrogenation of avermectins B1a and B1b catalyzed by RhCl(Ph3P)3 complexes was studied in a temperature range of 298–328 K at 275.7 kN m2, using catalyst loading in the range of 0.75–7.25 wt.% with respect to the avermectins in toluene solution. The effects on the hydrogenation rate of the catalyst, avermectins, and hydrogen concentrations were determined under complete induction time suppression and without catalyst deactivation. Rate equations were developed for various kinetic schemes on the basis of the main steps suggested by Wilkinson for simple olefin hydrogenation and fitted to the experimental data. A statistical analysis of regression using three plausible mechanisms of reaction allows a discussion on the adequacy of the models to approach the observed half-order reaction with respect to the catalyst loading and first-order to avermectins and hydrogen concentrations. A reaction mechanism featuring non-extensive simple dissociation of the catalyst precursor and reaction pathway along the hydride route with the rate-determining olefin coordination step proved fair enough to describe the hydrogenation of this macrocyclic lactone. The physical reasonability of the equilibrium and kinetic parameters was also discussed.
Fil: Zgolicz, Patricia Daniela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Cabrera, Maria Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Grau, Ricardo José Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Materia
Avermectins
Hydrogenation
Wilkinson Catalyst
Rhodium Complexes
Kinetic Modeling
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:11336/26624
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Kinetics of the homogeneous hydrogenation of avermectins catalyzed by RhCl(Ph3P)3 complexesZgolicz, Patricia DanielaCabrera, Maria InesGrau, Ricardo José AntonioAvermectinsHydrogenationWilkinson CatalystRhodium ComplexesKinetic Modelinghttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2The kinetics of the hydrogenation of avermectins B1a and B1b catalyzed by RhCl(Ph3P)3 complexes was studied in a temperature range of 298–328 K at 275.7 kN m2, using catalyst loading in the range of 0.75–7.25 wt.% with respect to the avermectins in toluene solution. The effects on the hydrogenation rate of the catalyst, avermectins, and hydrogen concentrations were determined under complete induction time suppression and without catalyst deactivation. Rate equations were developed for various kinetic schemes on the basis of the main steps suggested by Wilkinson for simple olefin hydrogenation and fitted to the experimental data. A statistical analysis of regression using three plausible mechanisms of reaction allows a discussion on the adequacy of the models to approach the observed half-order reaction with respect to the catalyst loading and first-order to avermectins and hydrogen concentrations. A reaction mechanism featuring non-extensive simple dissociation of the catalyst precursor and reaction pathway along the hydride route with the rate-determining olefin coordination step proved fair enough to describe the hydrogenation of this macrocyclic lactone. The physical reasonability of the equilibrium and kinetic parameters was also discussed.Fil: Zgolicz, Patricia Daniela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Cabrera, Maria Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Grau, Ricardo José Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaElsevier Science2005-12info: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/11336/26624Zgolicz, Patricia Daniela; Cabrera, Maria Ines; Grau, Ricardo José Antonio; Kinetics of the homogeneous hydrogenation of avermectins catalyzed by RhCl(Ph3P)3 complexes; Elsevier Science; Applied Catalysis A: General; 283; 1-2; 12-2005; 99-1090926-860XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.apcata.2004.12.040info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0926860X05000037info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:58:56Zoai:ri.conicet.gov.ar:11336/26624instacron: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 09:58:56.762CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Kinetics of the homogeneous hydrogenation of avermectins catalyzed by RhCl(Ph3P)3 complexes
title Kinetics of the homogeneous hydrogenation of avermectins catalyzed by RhCl(Ph3P)3 complexes
spellingShingle Kinetics of the homogeneous hydrogenation of avermectins catalyzed by RhCl(Ph3P)3 complexes
Zgolicz, Patricia Daniela
Avermectins
Hydrogenation
Wilkinson Catalyst
Rhodium Complexes
Kinetic Modeling
title_short Kinetics of the homogeneous hydrogenation of avermectins catalyzed by RhCl(Ph3P)3 complexes
title_full Kinetics of the homogeneous hydrogenation of avermectins catalyzed by RhCl(Ph3P)3 complexes
title_fullStr Kinetics of the homogeneous hydrogenation of avermectins catalyzed by RhCl(Ph3P)3 complexes
title_full_unstemmed Kinetics of the homogeneous hydrogenation of avermectins catalyzed by RhCl(Ph3P)3 complexes
title_sort Kinetics of the homogeneous hydrogenation of avermectins catalyzed by RhCl(Ph3P)3 complexes
dc.creator.none.fl_str_mv Zgolicz, Patricia Daniela
Cabrera, Maria Ines
Grau, Ricardo José Antonio
author Zgolicz, Patricia Daniela
author_facet Zgolicz, Patricia Daniela
Cabrera, Maria Ines
Grau, Ricardo José Antonio
author_role author
author2 Cabrera, Maria Ines
Grau, Ricardo José Antonio
author2_role author
author
dc.subject.none.fl_str_mv Avermectins
Hydrogenation
Wilkinson Catalyst
Rhodium Complexes
Kinetic Modeling
topic Avermectins
Hydrogenation
Wilkinson Catalyst
Rhodium Complexes
Kinetic Modeling
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv The kinetics of the hydrogenation of avermectins B1a and B1b catalyzed by RhCl(Ph3P)3 complexes was studied in a temperature range of 298–328 K at 275.7 kN m2, using catalyst loading in the range of 0.75–7.25 wt.% with respect to the avermectins in toluene solution. The effects on the hydrogenation rate of the catalyst, avermectins, and hydrogen concentrations were determined under complete induction time suppression and without catalyst deactivation. Rate equations were developed for various kinetic schemes on the basis of the main steps suggested by Wilkinson for simple olefin hydrogenation and fitted to the experimental data. A statistical analysis of regression using three plausible mechanisms of reaction allows a discussion on the adequacy of the models to approach the observed half-order reaction with respect to the catalyst loading and first-order to avermectins and hydrogen concentrations. A reaction mechanism featuring non-extensive simple dissociation of the catalyst precursor and reaction pathway along the hydride route with the rate-determining olefin coordination step proved fair enough to describe the hydrogenation of this macrocyclic lactone. The physical reasonability of the equilibrium and kinetic parameters was also discussed.
Fil: Zgolicz, Patricia Daniela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Cabrera, Maria Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Grau, Ricardo José Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
description The kinetics of the hydrogenation of avermectins B1a and B1b catalyzed by RhCl(Ph3P)3 complexes was studied in a temperature range of 298–328 K at 275.7 kN m2, using catalyst loading in the range of 0.75–7.25 wt.% with respect to the avermectins in toluene solution. The effects on the hydrogenation rate of the catalyst, avermectins, and hydrogen concentrations were determined under complete induction time suppression and without catalyst deactivation. Rate equations were developed for various kinetic schemes on the basis of the main steps suggested by Wilkinson for simple olefin hydrogenation and fitted to the experimental data. A statistical analysis of regression using three plausible mechanisms of reaction allows a discussion on the adequacy of the models to approach the observed half-order reaction with respect to the catalyst loading and first-order to avermectins and hydrogen concentrations. A reaction mechanism featuring non-extensive simple dissociation of the catalyst precursor and reaction pathway along the hydride route with the rate-determining olefin coordination step proved fair enough to describe the hydrogenation of this macrocyclic lactone. The physical reasonability of the equilibrium and kinetic parameters was also discussed.
publishDate 2005
dc.date.none.fl_str_mv 2005-12
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/11336/26624
Zgolicz, Patricia Daniela; Cabrera, Maria Ines; Grau, Ricardo José Antonio; Kinetics of the homogeneous hydrogenation of avermectins catalyzed by RhCl(Ph3P)3 complexes; Elsevier Science; Applied Catalysis A: General; 283; 1-2; 12-2005; 99-109
0926-860X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/26624
identifier_str_mv Zgolicz, Patricia Daniela; Cabrera, Maria Ines; Grau, Ricardo José Antonio; Kinetics of the homogeneous hydrogenation of avermectins catalyzed by RhCl(Ph3P)3 complexes; Elsevier Science; Applied Catalysis A: General; 283; 1-2; 12-2005; 99-109
0926-860X
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.apcata.2004.12.040
info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0926860X05000037
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 Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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_ 1844613752831344640
score 13.070432

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