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

The chemistry of late transition metal alkylidenes [M=CR], 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 PhC that allow either i...

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Authors: Campos, Jesús, Carmona, Ernesto
Format: article
Status:Published version
Publication Date:2017
Country:España
Institution:Consejo Superior de Investigaciones Científicas (CSIC)
Repository:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/159772
Online Access:http://hdl.handle.net/10261/159772
Access Level:Open access
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repository_id_str
spelling Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactionsCampos, JesúsCarmona, ErnestoThe chemistry of late transition metal alkylidenes [M=CR], 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 PhC 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 (η-CMe)Ir(III) complexes that bear a cyclo-metalated PMeXyl ligand (Xyl = 2,6-MeCH). The contribution of different monoanionic ligands (chloride, alkyl or hydride) to either stabilize the Ir=CR linkage or provide facile reactivity routes has been investigated, including the use of various deuterium isotopologues of the iridium complex precursors.Sociedad Química de MéxicoConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2018201820172018info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/159772reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Españolhttp://ref.scielo.org/4f4bxnSíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1597722026-05-22T06:33:51Z
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
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, Ernesto
author Campos, Jesús
author_facet Campos, Jesús
Carmona, Ernesto
author_role author
author2 Carmona, Ernesto
author2_role author
dc.contributor.none.fl_str_mv Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description The chemistry of late transition metal alkylidenes [M=CR], 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 PhC 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 (η-CMe)Ir(III) complexes that bear a cyclo-metalated PMeXyl ligand (Xyl = 2,6-MeCH). The contribution of different monoanionic ligands (chloride, alkyl or hydride) to either stabilize the Ir=CR 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
2018
2018
2018
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/159772
url http://hdl.handle.net/10261/159772
dc.language.none.fl_str_mv Español
language_invalid_str_mv Español
dc.relation.none.fl_str_mv http://ref.scielo.org/4f4bxn
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
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:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.811543

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