Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions

The chemistry of late transition metal alkylidenes [M=CR2], where R is H a hydrocarbyl group, have attracted widespread attention although mainly with reference to complexes of metals in low oxidation state. We focus in this paper on reactions based on electrophilic attacks by Ph3C+ that allow eithe...

Descripción completa

Detalles Bibliográficos
Autores: Campos, Jesús, Carmona Guzmán, Ernesto
Tipo de recurso: artículo
Estado:Versión enviada para evaluación y publicación
Fecha de publicación:2017
País:España
Institución:Universidad de Sevilla (US)
Repositorio:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:idus.us.es:11441/74582
Acceso en línea:https://hdl.handle.net/11441/74582
https://doi.org/10.29356/jmcs.v61i2.254
Access Level:acceso abierto
Palabra clave:Alkylidene
Hydride abstraction
Iridium
C-C coupling
Metalacycle
id ES_aed4e33abebc5f4d466dcb4c04b09c7f
oai_identifier_str oai:idus.us.es:11441/74582
network_acronym_str ES
network_name_str España
repository_id_str
spelling Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactionsCampos, JesúsCarmona Guzmán, ErnestoAlkylideneHydride abstractionIridiumC-C couplingMetalacycleThe chemistry of late transition metal alkylidenes [M=CR2], where R is H a hydrocarbyl group, have attracted widespread attention although mainly with reference to complexes of metals in low oxidation state. We focus in this paper on reactions based on electrophilic attacks by Ph3C+ that allow either isolation of stable cationic Ir(III) alkylidenes, considerably more attractive than well-known Ir(I) counterparts, or the generation of very reactive variants that experience fast migratory insertion into existing Ir-C and Ir-H sigma bonds. The present studies are based on (η5-C5Me5)Ir(III) complexes that bear a cyclometalated PMeXyl2 ligand (Xyl = 2,6-Me2C6H3). The contribution of different monoanionic ligands (chloride, alkyl or hydride) to either stabilize the Ir=CR2 linkage or provide facile reactivity routes has been investigated, including the use of various deuterium isotopologues of the iridium complex precursors.Sociedad Química de MéxicoQuímica Inorgánica2017info:eu-repo/semantics/articleinfo:eu-repo/semantics/submittedVersionapplication/pdfapplication/pdfhttps://hdl.handle.net/11441/74582https://doi.org/10.29356/jmcs.v61i2.254reponame:idUS. Depósito de Investigación de la Universidad de Sevillainstname:Universidad de Sevilla (US)InglésJournal of the Mexican Chemical Society, 61 (2), 77-88.http://dx.doi.org/10.29356/jmcs.v61i2.254info:eu-repo/semantics/openAccessoai:idus.us.es:11441/745822026-06-17T12:51:07Z
dc.title.none.fl_str_mv Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions
title Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions
spellingShingle Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions
Campos, Jesús
Alkylidene
Hydride abstraction
Iridium
C-C coupling
Metalacycle
title_short Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions
title_full Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions
title_fullStr Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions
title_full_unstemmed Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions
title_sort Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions
dc.creator.none.fl_str_mv Campos, Jesús
Carmona Guzmán, Ernesto
author Campos, Jesús
author_facet Campos, Jesús
Carmona Guzmán, Ernesto
author_role author
author2 Carmona Guzmán, Ernesto
author2_role author
dc.contributor.none.fl_str_mv Química Inorgánica
dc.subject.none.fl_str_mv Alkylidene
Hydride abstraction
Iridium
C-C coupling
Metalacycle
topic Alkylidene
Hydride abstraction
Iridium
C-C coupling
Metalacycle
description The chemistry of late transition metal alkylidenes [M=CR2], where R is H a hydrocarbyl group, have attracted widespread attention although mainly with reference to complexes of metals in low oxidation state. We focus in this paper on reactions based on electrophilic attacks by Ph3C+ that allow either isolation of stable cationic Ir(III) alkylidenes, considerably more attractive than well-known Ir(I) counterparts, or the generation of very reactive variants that experience fast migratory insertion into existing Ir-C and Ir-H sigma bonds. The present studies are based on (η5-C5Me5)Ir(III) complexes that bear a cyclometalated PMeXyl2 ligand (Xyl = 2,6-Me2C6H3). The contribution of different monoanionic ligands (chloride, alkyl or hydride) to either stabilize the Ir=CR2 linkage or provide facile reactivity routes has been investigated, including the use of various deuterium isotopologues of the iridium complex precursors.
publishDate 2017
dc.date.none.fl_str_mv 2017
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/submittedVersion
format article
status_str submittedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/11441/74582
https://doi.org/10.29356/jmcs.v61i2.254
url https://hdl.handle.net/11441/74582
https://doi.org/10.29356/jmcs.v61i2.254
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Journal of the Mexican Chemical Society, 61 (2), 77-88.
http://dx.doi.org/10.29356/jmcs.v61i2.254
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Sociedad Química de México
publisher.none.fl_str_mv Sociedad Química de México
dc.source.none.fl_str_mv reponame:idUS. Depósito de Investigación de la Universidad de Sevilla
instname:Universidad de Sevilla (US)
instname_str Universidad de Sevilla (US)
reponame_str idUS. Depósito de Investigación de la Universidad de Sevilla
collection idUS. Depósito de Investigación de la Universidad de Sevilla
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869416614427885568
score 15,300719

Similares en LA Referencia