Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions

V imido alkylidenes have been applied for the ring-opening metathesis polymerization involving cyclic olefins. However, those complexes found limited application in reactions with acyclic terminal olefins due to instability toward ethylene. Experimental and theoretical studies show that the β-hydrid...

Descripción completa

Detalles Bibliográficos
Autores: Belov, Dmitry S., Fenoll, Didac A.|||0000-0003-1141-8114, Chakraborty, Indranil|||0000-0003-2842-211X, Solans-Monfort, Xavier|||0000-0002-2172-3895, Bukhryakov, Konstantin V.|||0000-0002-8425-9671
Tipo de recurso: artículo
Fecha de publicación:2021
País:España
Institución:Universitat Autònoma de Barcelona
Repositorio:Dipòsit Digital de Documents de la UAB
Idioma:inglés
OAI Identifier:oai:ddd.uab.cat:280631
Acceso en línea:https://ddd.uab.cat/record/280631
https://dx.doi.org/urn:doi:10.1021/acs.organomet.1c00425
Access Level:acceso abierto
id ES_2eadf44f73879b4402ade366f357efa7
oai_identifier_str oai:ddd.uab.cat:280631
network_acronym_str ES
network_name_str España
repository_id_str
spelling Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis ReactionsBelov, Dmitry S.Fenoll, Didac A.|||0000-0003-1141-8114Chakraborty, Indranil|||0000-0003-2842-211XSolans-Monfort, Xavier|||0000-0002-2172-3895Bukhryakov, Konstantin V.|||0000-0002-8425-9671V imido alkylidenes have been applied for the ring-opening metathesis polymerization involving cyclic olefins. However, those complexes found limited application in reactions with acyclic terminal olefins due to instability toward ethylene. Experimental and theoretical studies show that the β-hydride elimination from unsubstituted metallacyclobutene is the primary decomposition pathway in those systems. Herein, we report the synthesis of the first catalytically active V oxo alkylidene, VO(CHSiMe3)(PEt3)2Cl, which exhibits the highest reported productivity with various terminal olefins in ring-closing metathesis reactions among known V catalysts. Presented DFT studies indicate that β-hydride elimination is significantly disfavored for V oxo species. 22021-01-0120212021-01-01Articlehttp://purl.org/coar/resource_type/c_6501AMhttp://purl.org/coar/version/c_ab4af688f83e57aainfo:eu-repo/semantics/articleapplication/pdfhttps://ddd.uab.cat/record/280631https://dx.doi.org/urn:doi:10.1021/acs.organomet.1c00425reponame:Dipòsit Digital de Documents de la UABinstname:Universitat Autònoma de BarcelonaInglésengAgencia Estatal de Investigación https://doi.org/10.13039/501100011033 PID2020-112715GB-I00Agència de Gestió d'Ajuts Universitaris i de Recerca https://doi.org/10.13039/501100003030 2017/SGR-1323open accesshttp://purl.org/coar/access_right/c_abf2Aquest material està protegit per drets d'autor i/o drets afins. Podeu utilitzar aquest material en funció del que permet la legislació de drets d'autor i drets afins d'aplicació al vostre cas. Per a d'altres usos heu d'obtenir permís del(s) titular(s) de drets.https://rightsstatements.org/vocab/InC/1.0/info:eu-repo/semantics/openAccessoai:ddd.uab.cat:2806312026-06-06T12:50:31Z
dc.title.none.fl_str_mv Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions
title Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions
spellingShingle Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions
Belov, Dmitry S.
title_short Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions
title_full Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions
title_fullStr Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions
title_full_unstemmed Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions
title_sort Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions
dc.creator.none.fl_str_mv Belov, Dmitry S.
Fenoll, Didac A.|||0000-0003-1141-8114
Chakraborty, Indranil|||0000-0003-2842-211X
Solans-Monfort, Xavier|||0000-0002-2172-3895
Bukhryakov, Konstantin V.|||0000-0002-8425-9671
author Belov, Dmitry S.
author_facet Belov, Dmitry S.
Fenoll, Didac A.|||0000-0003-1141-8114
Chakraborty, Indranil|||0000-0003-2842-211X
Solans-Monfort, Xavier|||0000-0002-2172-3895
Bukhryakov, Konstantin V.|||0000-0002-8425-9671
author_role author
author2 Fenoll, Didac A.|||0000-0003-1141-8114
Chakraborty, Indranil|||0000-0003-2842-211X
Solans-Monfort, Xavier|||0000-0002-2172-3895
Bukhryakov, Konstantin V.|||0000-0002-8425-9671
author2_role author
author
author
author
description V imido alkylidenes have been applied for the ring-opening metathesis polymerization involving cyclic olefins. However, those complexes found limited application in reactions with acyclic terminal olefins due to instability toward ethylene. Experimental and theoretical studies show that the β-hydride elimination from unsubstituted metallacyclobutene is the primary decomposition pathway in those systems. Herein, we report the synthesis of the first catalytically active V oxo alkylidene, VO(CHSiMe3)(PEt3)2Cl, which exhibits the highest reported productivity with various terminal olefins in ring-closing metathesis reactions among known V catalysts. Presented DFT studies indicate that β-hydride elimination is significantly disfavored for V oxo species.
publishDate 2021
dc.date.none.fl_str_mv 2
2021-01-01
2021
2021-01-01
dc.type.none.fl_str_mv Article
http://purl.org/coar/resource_type/c_6501
AM
http://purl.org/coar/version/c_ab4af688f83e57aa
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://ddd.uab.cat/record/280631
https://dx.doi.org/urn:doi:10.1021/acs.organomet.1c00425
url https://ddd.uab.cat/record/280631
https://dx.doi.org/urn:doi:10.1021/acs.organomet.1c00425
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Agencia Estatal de Investigación https://doi.org/10.13039/501100011033 PID2020-112715GB-I00
Agència de Gestió d'Ajuts Universitaris i de Recerca https://doi.org/10.13039/501100003030 2017/SGR-1323
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
https://rightsstatements.org/vocab/InC/1.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
https://rightsstatements.org/vocab/InC/1.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:Dipòsit Digital de Documents de la UAB
instname:Universitat Autònoma de Barcelona
instname_str Universitat Autònoma de Barcelona
reponame_str Dipòsit Digital de Documents de la UAB
collection Dipòsit Digital de Documents de la UAB
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869405426883231744
score 15,301629

Similares en LA Referencia