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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/26624
Ver los metadatos del registro completo
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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 Técnicas2025-09-03T09:55:45Zoai: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:34982025-09-03 09:55:46.064CONICET 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 |
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1842269365103230976 |
score |
13.13397 |