Role of the hydrophobicity on the thermodynamic and kinetic acidity of Fischer thiocarbene complexes

Autores
Andrada, Diego Marcelo; Zoloff Michoff, Martin Eduardo; de Rossi, Rita H.; Granados, Alejandro Manuel
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Rate constants for the reversible deprotonation of (CO)5W=C(SR)CH3 (W-SR) by OH−, water and a number of primary aliphatic and secondary alicyclic amines, have been determined in 50% MeCN: 50% water at 25 °C. In addition, solvation energy and proton affinities values for M-SR (M = Cr and W) in the gas phase and in acetonitrile have been computed at DFT level. Although there is not a linear correlation between the calculated proton affinities and the measured pKas, the calculations reveal that when solvent effects are taken into account the substituted compounds studied show differences in their proton affinities. There is a good correlation between the change in cavitation energy (ΔGcav) for the Fischer carbene complexes and log P of the thioalkyl substituents. In proton transfer reactions with amines, steric effects are more important for W complexes with respect to their Cr analogues as a consequence of differences in transition state progress. On the other hand, in reactions with OH−, hydrophobicity of the R substituent is responsible for the observed changes in intrinsic kinetic acidities, which is supported by the good correlation obtained between log k0 and log P. W complexes are more sensitive to hydrophobic effects due to the tighter solvation sphere with respect to their Cr counterparts. However, in the limit of log P = 0, the energy involved in the solvent reorganization process is the same regardless of the metal.
Fil: Andrada, Diego Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Zoloff Michoff, Martin Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: de Rossi, Rita H.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Granados, Alejandro Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
FISCHER CARBENE COMPLEXES
KINETICS
HYDROPHOBICITY
SOLVATION
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:11336/186375
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/186375
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Role of the hydrophobicity on the thermodynamic and kinetic acidity of Fischer thiocarbene complexesAndrada, Diego MarceloZoloff Michoff, Martin Eduardode Rossi, Rita H.Granados, Alejandro ManuelFISCHER CARBENE COMPLEXESKINETICSHYDROPHOBICITYSOLVATIONhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Rate constants for the reversible deprotonation of (CO)5W=C(SR)CH3 (W-SR) by OH−, water and a number of primary aliphatic and secondary alicyclic amines, have been determined in 50% MeCN: 50% water at 25 °C. In addition, solvation energy and proton affinities values for M-SR (M = Cr and W) in the gas phase and in acetonitrile have been computed at DFT level. Although there is not a linear correlation between the calculated proton affinities and the measured pKas, the calculations reveal that when solvent effects are taken into account the substituted compounds studied show differences in their proton affinities. There is a good correlation between the change in cavitation energy (ΔGcav) for the Fischer carbene complexes and log P of the thioalkyl substituents. In proton transfer reactions with amines, steric effects are more important for W complexes with respect to their Cr analogues as a consequence of differences in transition state progress. On the other hand, in reactions with OH−, hydrophobicity of the R substituent is responsible for the observed changes in intrinsic kinetic acidities, which is supported by the good correlation obtained between log k0 and log P. W complexes are more sensitive to hydrophobic effects due to the tighter solvation sphere with respect to their Cr counterparts. However, in the limit of log P = 0, the energy involved in the solvent reorganization process is the same regardless of the metal.Fil: Andrada, Diego Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Zoloff Michoff, Martin Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: de Rossi, Rita H.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Granados, Alejandro Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaRoyal Society of Chemistry2010-04info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/186375Andrada, Diego Marcelo; Zoloff Michoff, Martin Eduardo; de Rossi, Rita H.; Granados, Alejandro Manuel; Role of the hydrophobicity on the thermodynamic and kinetic acidity of Fischer thiocarbene complexes; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 12; 25; 4-2010; 6616-66241463-9076CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2010/cp/c000141dinfo:eu-repo/semantics/altIdentifier/doi/10.1039/C000141Dinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:16:59Zoai:ri.conicet.gov.ar:11336/186375instacron: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:34982025-10-22 11:16:59.741CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Role of the hydrophobicity on the thermodynamic and kinetic acidity of Fischer thiocarbene complexes
title Role of the hydrophobicity on the thermodynamic and kinetic acidity of Fischer thiocarbene complexes
spellingShingle Role of the hydrophobicity on the thermodynamic and kinetic acidity of Fischer thiocarbene complexes
Andrada, Diego Marcelo
FISCHER CARBENE COMPLEXES
KINETICS
HYDROPHOBICITY
SOLVATION
title_short Role of the hydrophobicity on the thermodynamic and kinetic acidity of Fischer thiocarbene complexes
title_full Role of the hydrophobicity on the thermodynamic and kinetic acidity of Fischer thiocarbene complexes
title_fullStr Role of the hydrophobicity on the thermodynamic and kinetic acidity of Fischer thiocarbene complexes
title_full_unstemmed Role of the hydrophobicity on the thermodynamic and kinetic acidity of Fischer thiocarbene complexes
title_sort Role of the hydrophobicity on the thermodynamic and kinetic acidity of Fischer thiocarbene complexes
dc.creator.none.fl_str_mv Andrada, Diego Marcelo
Zoloff Michoff, Martin Eduardo
de Rossi, Rita H.
Granados, Alejandro Manuel
author Andrada, Diego Marcelo
author_facet Andrada, Diego Marcelo
Zoloff Michoff, Martin Eduardo
de Rossi, Rita H.
Granados, Alejandro Manuel
author_role author
author2 Zoloff Michoff, Martin Eduardo
de Rossi, Rita H.
Granados, Alejandro Manuel
author2_role author
author
author
dc.subject.none.fl_str_mv FISCHER CARBENE COMPLEXES
KINETICS
HYDROPHOBICITY
SOLVATION
topic FISCHER CARBENE COMPLEXES
KINETICS
HYDROPHOBICITY
SOLVATION
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Rate constants for the reversible deprotonation of (CO)5W=C(SR)CH3 (W-SR) by OH−, water and a number of primary aliphatic and secondary alicyclic amines, have been determined in 50% MeCN: 50% water at 25 °C. In addition, solvation energy and proton affinities values for M-SR (M = Cr and W) in the gas phase and in acetonitrile have been computed at DFT level. Although there is not a linear correlation between the calculated proton affinities and the measured pKas, the calculations reveal that when solvent effects are taken into account the substituted compounds studied show differences in their proton affinities. There is a good correlation between the change in cavitation energy (ΔGcav) for the Fischer carbene complexes and log P of the thioalkyl substituents. In proton transfer reactions with amines, steric effects are more important for W complexes with respect to their Cr analogues as a consequence of differences in transition state progress. On the other hand, in reactions with OH−, hydrophobicity of the R substituent is responsible for the observed changes in intrinsic kinetic acidities, which is supported by the good correlation obtained between log k0 and log P. W complexes are more sensitive to hydrophobic effects due to the tighter solvation sphere with respect to their Cr counterparts. However, in the limit of log P = 0, the energy involved in the solvent reorganization process is the same regardless of the metal.
Fil: Andrada, Diego Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Zoloff Michoff, Martin Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: de Rossi, Rita H.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Granados, Alejandro Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description Rate constants for the reversible deprotonation of (CO)5W=C(SR)CH3 (W-SR) by OH−, water and a number of primary aliphatic and secondary alicyclic amines, have been determined in 50% MeCN: 50% water at 25 °C. In addition, solvation energy and proton affinities values for M-SR (M = Cr and W) in the gas phase and in acetonitrile have been computed at DFT level. Although there is not a linear correlation between the calculated proton affinities and the measured pKas, the calculations reveal that when solvent effects are taken into account the substituted compounds studied show differences in their proton affinities. There is a good correlation between the change in cavitation energy (ΔGcav) for the Fischer carbene complexes and log P of the thioalkyl substituents. In proton transfer reactions with amines, steric effects are more important for W complexes with respect to their Cr analogues as a consequence of differences in transition state progress. On the other hand, in reactions with OH−, hydrophobicity of the R substituent is responsible for the observed changes in intrinsic kinetic acidities, which is supported by the good correlation obtained between log k0 and log P. W complexes are more sensitive to hydrophobic effects due to the tighter solvation sphere with respect to their Cr counterparts. However, in the limit of log P = 0, the energy involved in the solvent reorganization process is the same regardless of the metal.
publishDate 2010
dc.date.none.fl_str_mv 2010-04
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/11336/186375
Andrada, Diego Marcelo; Zoloff Michoff, Martin Eduardo; de Rossi, Rita H.; Granados, Alejandro Manuel; Role of the hydrophobicity on the thermodynamic and kinetic acidity of Fischer thiocarbene complexes; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 12; 25; 4-2010; 6616-6624
1463-9076
CONICET Digital
CONICET
url http://hdl.handle.net/11336/186375
identifier_str_mv Andrada, Diego Marcelo; Zoloff Michoff, Martin Eduardo; de Rossi, Rita H.; Granados, Alejandro Manuel; Role of the hydrophobicity on the thermodynamic and kinetic acidity of Fischer thiocarbene complexes; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 12; 25; 4-2010; 6616-6624
1463-9076
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://pubs.rsc.org/en/content/articlelanding/2010/cp/c000141d
info:eu-repo/semantics/altIdentifier/doi/10.1039/C000141D
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
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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 12.982451

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