Direct detection of key intermediates in rhodium(I)-catalyzed [2+2+2] cycloadditions of alkynes by ESI-MS

The mechanism of the Rh-catalysed [2+2+2] cycloaddition reaction of diynes with monoynes has been examined using ESI-MS and ESI-CID-MS analysis. The catalytic system used consisted of the combination of a cationic rhodium(I) complex with bisphosphine ligands, which generates highly active complexes...

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Autores: Parera Briansó, Magda, Dachs Soler, Anna, Solà i Puig, Miquel, Pla i Quintana, Anna, Roglans i Ribas, Anna
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2012
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/11342
Acceso en línea:http://hdl.handle.net/10256/11342
Access Level:acceso embargado
Palabra clave:Reaccions d'addició
Addition reactions
Catalitzadors de rodi
Rhodium catalyst
Espectrometria de masses
Mass spectrometry
Rodi
Rhodium
Funcional de densitat, Teoria del
Density functionals
Ciclització (Química)
Ring formation (Chemistry)
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spelling Direct detection of key intermediates in rhodium(I)-catalyzed [2+2+2] cycloadditions of alkynes by ESI-MSParera Briansó, MagdaDachs Soler, AnnaSolà i Puig, MiquelPla i Quintana, AnnaRoglans i Ribas, AnnaReaccions d'addicióAddition reactionsCatalitzadors de rodiRhodium catalystEspectrometria de massesMass spectrometryRodiRhodiumFuncional de densitat, Teoria delDensity functionalsCiclització (Química)Ring formation (Chemistry)The mechanism of the Rh-catalysed [2+2+2] cycloaddition reaction of diynes with monoynes has been examined using ESI-MS and ESI-CID-MS analysis. The catalytic system used consisted of the combination of a cationic rhodium(I) complex with bisphosphine ligands, which generates highly active complexes that can be detected by ESI(+) experiments. ESI-MS on-line monitoring has allowed the detection for the first time of all of the intermediates in the catalytic cycle, supporting the mechanistic proposal based mainly on theoretical calculations. For all ESI-MS experiments, the structural assignments of ions are supported by tandem mass spectrometry analyses. Computer model studies based on density functional theory (DFT) support the structural proposal made for the monoyne insertion intermediate. The collective studies provide new insight into the reactivity of cationic rhodacyclopentadienes, which should facilitate the design of related rhodium-catalysed C-C couplings. Detecting intermediates: The mechanism of the Rh I-catalyzed [2+2+2] cycloaddition reaction was examined using ESI-MS (see scheme). All of the intermediates in the catalytic cycle were detected by ESI-MS for the first time and characterized by ESI-MS/MS. DFT was used to support the structural proposal made for the monoyne insertion intermediateFinancial support from the Spanish Ministry of Education and Science (MEC) (Projects Nos.: CTQ2011-23121/BQU and CTQ2011-23156/BQU) and the DIUE of the Generalitat de Catalunya (Project No.: 2009SGR637) is gratefully acknowledged. M. P. thanks the Generalitat de Catalunya for a predoctoral grant. We would also like to thank Anna Costa for her technical assistance with the ESI mass spectrometer and Jesus Orduna for helpful discussions. Excellent service by the Centre de Serveis Cientifics i Academics de Catalunya (CESCA) is gratefully acknowledged. Support for the research of M. S. was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE of the Generalitat de CatalunyaWiley-VCH VerlagMinisterio de Ciencia e Innovación (Espanya)Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recercainfoinfo2012info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10256/11342http://hdl.handle.net/10256/11342© Chemistry - A European Journal, 2012, vol. 18, núm. 41, p. 13097-13107Articles publicats (D-Q)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1002/chem.201200880info:eu-repo/semantics/altIdentifier/issn/0947-6539info:eu-repo/semantics/altIdentifier/eissn/1521-3765info:eu-repo/grantAgreement/MICINN//CTQ2011-23121info:eu-repo/grantAgreement/MICINN//CTQ2011-23156AGAUR/2009-2014/2009 SGR-637Tots els drets reservatsinfo:eu-repo/semantics/embargoedAccessoai:recercat.cat:10256/113422026-05-29T05:05:01Z
dc.title.none.fl_str_mv Direct detection of key intermediates in rhodium(I)-catalyzed [2+2+2] cycloadditions of alkynes by ESI-MS
title Direct detection of key intermediates in rhodium(I)-catalyzed [2+2+2] cycloadditions of alkynes by ESI-MS
spellingShingle Direct detection of key intermediates in rhodium(I)-catalyzed [2+2+2] cycloadditions of alkynes by ESI-MS
Parera Briansó, Magda
Reaccions d'addició
Addition reactions
Catalitzadors de rodi
Rhodium catalyst
Espectrometria de masses
Mass spectrometry
Rodi
Rhodium
Funcional de densitat, Teoria del
Density functionals
Ciclització (Química)
Ring formation (Chemistry)
title_short Direct detection of key intermediates in rhodium(I)-catalyzed [2+2+2] cycloadditions of alkynes by ESI-MS
title_full Direct detection of key intermediates in rhodium(I)-catalyzed [2+2+2] cycloadditions of alkynes by ESI-MS
title_fullStr Direct detection of key intermediates in rhodium(I)-catalyzed [2+2+2] cycloadditions of alkynes by ESI-MS
title_full_unstemmed Direct detection of key intermediates in rhodium(I)-catalyzed [2+2+2] cycloadditions of alkynes by ESI-MS
title_sort Direct detection of key intermediates in rhodium(I)-catalyzed [2+2+2] cycloadditions of alkynes by ESI-MS
dc.creator.none.fl_str_mv Parera Briansó, Magda
Dachs Soler, Anna
Solà i Puig, Miquel
Pla i Quintana, Anna
Roglans i Ribas, Anna
author Parera Briansó, Magda
author_facet Parera Briansó, Magda
Dachs Soler, Anna
Solà i Puig, Miquel
Pla i Quintana, Anna
Roglans i Ribas, Anna
author_role author
author2 Dachs Soler, Anna
Solà i Puig, Miquel
Pla i Quintana, Anna
Roglans i Ribas, Anna
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (Espanya)
Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recerca
dc.subject.none.fl_str_mv Reaccions d'addició
Addition reactions
Catalitzadors de rodi
Rhodium catalyst
Espectrometria de masses
Mass spectrometry
Rodi
Rhodium
Funcional de densitat, Teoria del
Density functionals
Ciclització (Química)
Ring formation (Chemistry)
topic Reaccions d'addició
Addition reactions
Catalitzadors de rodi
Rhodium catalyst
Espectrometria de masses
Mass spectrometry
Rodi
Rhodium
Funcional de densitat, Teoria del
Density functionals
Ciclització (Química)
Ring formation (Chemistry)
description The mechanism of the Rh-catalysed [2+2+2] cycloaddition reaction of diynes with monoynes has been examined using ESI-MS and ESI-CID-MS analysis. The catalytic system used consisted of the combination of a cationic rhodium(I) complex with bisphosphine ligands, which generates highly active complexes that can be detected by ESI(+) experiments. ESI-MS on-line monitoring has allowed the detection for the first time of all of the intermediates in the catalytic cycle, supporting the mechanistic proposal based mainly on theoretical calculations. For all ESI-MS experiments, the structural assignments of ions are supported by tandem mass spectrometry analyses. Computer model studies based on density functional theory (DFT) support the structural proposal made for the monoyne insertion intermediate. The collective studies provide new insight into the reactivity of cationic rhodacyclopentadienes, which should facilitate the design of related rhodium-catalysed C-C couplings. Detecting intermediates: The mechanism of the Rh I-catalyzed [2+2+2] cycloaddition reaction was examined using ESI-MS (see scheme). All of the intermediates in the catalytic cycle were detected by ESI-MS for the first time and characterized by ESI-MS/MS. DFT was used to support the structural proposal made for the monoyne insertion intermediate
publishDate 2012
dc.date.none.fl_str_mv 2012
info
info
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/11342
http://hdl.handle.net/10256/11342
url http://hdl.handle.net/10256/11342
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.201200880
info:eu-repo/semantics/altIdentifier/issn/0947-6539
info:eu-repo/semantics/altIdentifier/eissn/1521-3765
info:eu-repo/grantAgreement/MICINN//CTQ2011-23121
info:eu-repo/grantAgreement/MICINN//CTQ2011-23156
AGAUR/2009-2014/2009 SGR-637
dc.rights.none.fl_str_mv Tots els drets reservats
info:eu-repo/semantics/embargoedAccess
rights_invalid_str_mv Tots els drets reservats
eu_rights_str_mv embargoedAccess
dc.format.none.fl_str_mv 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 © Chemistry - A European Journal, 2012, vol. 18, núm. 41, p. 13097-13107
Articles publicats (D-Q)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,81155

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