Amide-directed formation of five-coordinate osmium alkylidenes from alkynes

This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

Detalles Bibliográficos
Autores: Casanova, Noelia, Esteruelas, Miguel A., Gulías, Moisés, Larramona, Carmen, Mascareñas, José L., Oñate, Enrique
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2016
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/128037
Acceso en línea:http://hdl.handle.net/10261/128037
Access Level:acceso abierto
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spelling Amide-directed formation of five-coordinate osmium alkylidenes from alkynesCasanova, NoeliaEsteruelas, Miguel A.Gulías, MoisésLarramona, CarmenMascareñas, José L.Oñate, EnriqueThis is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.The amide-directed synthesis of five-coordinate osmium alkylidene derivatives from alkynes is reported. These types of complexes, which have been elusive until now because of the tendency of osmium to give hydride alkylidyne species, are prepared by reaction of the dihydride OsH2Cl2(PiPr3)2 (1) with terminal alkynes containing a distal amide group. Complex 1 reacts with N-phenylhex-5-ynamide and N-phenylhepta-6-ynamide to give OsCl2{═C(CH3)(CH2)nNH(CO)Ph}(PiPr3)2 (n = 3 (2), 4 (3)). The relative position of carbonyl and NH groups in the organic substrates has no influence on the reaction. Thus, treatment of 1 with N-(pent-4-yn-1-yl)benzamide leads to OsCl2{═C(CH3)(CH2)3NHC(O)Ph}(PiPr3)2 (4). The new compounds are intermediate species in the cleavage of the C–C triple bond of the alkynes. Under mild conditions, they undergo the rupture of the Cα–CH3 bond of the alkylidene, which comes from the alkyne triple bond, to afford six-coordinate hydride–alkylidyne derivatives. In dichloromethane, complex 2 gives a 10:7 mixture of OsHCl2{≡C(CH2)3C(O)NHPh}(PiPr3)2 (5) and OsHCl2{≡CCH(CH3)(CH2)2C(O)NHPh}(PiPr3)2 (6). The first complex contains a linear separation between the alkylidyne Cα atom and the amide group, whereas the spacer is branched in the second complex. In contrast to the case for 2, complex 4 selectively affords OsHCl2{≡C(CH2)3NHC(O)Ph}(PiPr3)2 (7). In spite of their instability, these compounds give the alkylidene–allene metathesis, being a useful entry to five-coordinate vinylidene complexes, including the dicarbon-disubstituted OsCl2(═C═CMe2)(PiPr3)2 (8) and the monosubstituted OsCl2(═C═CHCy)(PiPr3)2 (9).Financial support from the Spanish MINECO (Projects CTQ2014-52799-P, SAF2013-41943-R, and CTQ2014-51912-REDC), the DGA (E35), the ERDF, the European Research Council (Advanced Grant No. 340055) and the European Social Fund (FSE), and the Xunta de Galicia (grants GRC2013-041, EM2013/036, 2015-CP082 and a Parga Pondal contract to M.G.) is acknowledged.Peer reviewedAmerican Chemical SocietyMinisterio de Economía y Competitividad (España)Diputación General de AragónEuropean Research CouncilEuropean CommissionXunta de GaliciaConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]201620162016info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/128037reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/EC/FP7/340055info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2014-52799-Pinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/SAF2013-41943-Rinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2014-51912-REDChttp://dx.doi.org/10.1021/acs.organomet.5b00777Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1280372026-05-22T06:33:51Z
dc.title.none.fl_str_mv Amide-directed formation of five-coordinate osmium alkylidenes from alkynes
title Amide-directed formation of five-coordinate osmium alkylidenes from alkynes
spellingShingle Amide-directed formation of five-coordinate osmium alkylidenes from alkynes
Casanova, Noelia
title_short Amide-directed formation of five-coordinate osmium alkylidenes from alkynes
title_full Amide-directed formation of five-coordinate osmium alkylidenes from alkynes
title_fullStr Amide-directed formation of five-coordinate osmium alkylidenes from alkynes
title_full_unstemmed Amide-directed formation of five-coordinate osmium alkylidenes from alkynes
title_sort Amide-directed formation of five-coordinate osmium alkylidenes from alkynes
dc.creator.none.fl_str_mv Casanova, Noelia
Esteruelas, Miguel A.
Gulías, Moisés
Larramona, Carmen
Mascareñas, José L.
Oñate, Enrique
author Casanova, Noelia
author_facet Casanova, Noelia
Esteruelas, Miguel A.
Gulías, Moisés
Larramona, Carmen
Mascareñas, José L.
Oñate, Enrique
author_role author
author2 Esteruelas, Miguel A.
Gulías, Moisés
Larramona, Carmen
Mascareñas, José L.
Oñate, Enrique
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (España)
Diputación General de Aragón
European Research Council
European Commission
Xunta de Galicia
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
publishDate 2016
dc.date.none.fl_str_mv 2016
2016
2016
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/10261/128037
url http://hdl.handle.net/10261/128037
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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info:eu-repo/grantAgreement/EC/FP7/340055
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2014-52799-P
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/SAF2013-41943-R
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2014-51912-REDC
http://dx.doi.org/10.1021/acs.organomet.5b00777
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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)
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