Amide-Directed Formation of Five-Coordinate Osmium Alkylidenes from Alkynes

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...

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Autores: Casanova, N., Esteruelas, M. A., Gulías, M., Larramona, C., Mascareñas, J. L., Oñate, E.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2016
País:España
Institución:Universidad de Zaragoza
Repositorio:Zaguán. Repositorio Digital de la Universidad de Zaragoza
OAI Identifier:oai:zaguan.unizar.es:61429
Acceso en línea:http://zaguan.unizar.es/record/61429
Access Level:acceso abierto
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spelling Amide-Directed Formation of Five-Coordinate Osmium Alkylidenes from AlkynesCasanova, N.Esteruelas, M. A.Gulías, M.Larramona, C.Mascareñas, J. L.Oñate, E.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 Ca-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 Ca 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).2016info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://zaguan.unizar.es/record/61429reponame:Zaguán. Repositorio Digital de la Universidad de Zaragozainstname:Universidad de ZaragozaInglésinfo:eu-repo/grantAgreement/ES/MINECO/SAF2013-41943-Rinfo:eu-repo/grantAgreement/ES/MINECO/CTQ2014-52799-Pinfo:eu-repo/grantAgreement/ES/MINECO/CTQ2014-51912-REDCinfo:eu-repo/grantAgreement/EC/FP7/340055info:eu-repo/grantAgreement/ES/DGA/E35info:eu-repo/semantics/openAccessoai:zaguan.unizar.es:614292026-05-29T13:59:51Z
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, N.
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, N.
Esteruelas, M. A.
Gulías, M.
Larramona, C.
Mascareñas, J. L.
Oñate, E.
author Casanova, N.
author_facet Casanova, N.
Esteruelas, M. A.
Gulías, M.
Larramona, C.
Mascareñas, J. L.
Oñate, E.
author_role author
author2 Esteruelas, M. A.
Gulías, M.
Larramona, C.
Mascareñas, J. L.
Oñate, E.
author2_role author
author
author
author
author
description 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 Ca-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 Ca 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).
publishDate 2016
dc.date.none.fl_str_mv 2016
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status_str publishedVersion
dc.identifier.none.fl_str_mv http://zaguan.unizar.es/record/61429
url http://zaguan.unizar.es/record/61429
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/ES/MINECO/SAF2013-41943-R
info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-52799-P
info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-51912-REDC
info:eu-repo/grantAgreement/EC/FP7/340055
info:eu-repo/grantAgreement/ES/DGA/E35
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
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dc.source.none.fl_str_mv reponame:Zaguán. Repositorio Digital de la Universidad de Zaragoza
instname:Universidad de Zaragoza
instname_str Universidad de Zaragoza
reponame_str Zaguán. Repositorio Digital de la Universidad de Zaragoza
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