Osmium hydride acetylacetonate complexes and their application in acceptorless dehydrogenative coupling of alcohols and amines and for the dehydrogenation of cyclic amines

The preparation of new osmium hydride complexes, starting from OsH6(PiPr3)2 (1) and OsH2Cl2(PiPr3)2 (2), and their catalytic activity in acceptorless dehydrogenative coupling of alcohols and amines and in dehydrogenation of cyclic amines are reported. Complex 1 reacts with acetylacetone (Hacac) to g...

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Autores: Esteruelas, Miguel A., Lezáun, Virginia, Martínez, Antonio, Oliván, Montserrat, Oñate, Enrique
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2017
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/154601
Acceso en línea:http://hdl.handle.net/10261/154601
Access Level:acceso abierto
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spelling Osmium hydride acetylacetonate complexes and their application in acceptorless dehydrogenative coupling of alcohols and amines and for the dehydrogenation of cyclic aminesEsteruelas, Miguel A.Lezáun, VirginiaMartínez, AntonioOliván, MontserratOñate, EnriqueThe preparation of new osmium hydride complexes, starting from OsH6(PiPr3)2 (1) and OsH2Cl2(PiPr3)2 (2), and their catalytic activity in acceptorless dehydrogenative coupling of alcohols and amines and in dehydrogenation of cyclic amines are reported. Complex 1 reacts with acetylacetone (Hacac) to give the classical trihydride OsH3(acac)(PiPr3)2 (3). The protonation of 3 with triflic acid (HOTf) produces the release of H2 and the formation of the unsaturated osmium(IV) dihydride [OsH2(acac)(PiPr3)2]OTf (4), which is also prepared by starting from 2 via the intermediate OsH2Cl(acac)(PiPr3)2 (5). Treatment of an acetylacetone solution of 5 with KOH affords Os(acac)2(PiPr3)2 (6). In the presence of 5 mol % of KOH, complexes 3–6 promote the coupling of benzyl alcohol and aniline to give N-benzylideneaniline and H2. Under the same conditions, complex 3 catalyzes a wide range of analogous couplings to afford a variety of imines, including aliphatic imines, with yields between 90 and 40% after 1–48 h. Complex 3 also catalyzes the dehydrogenation of cyclic amines. According to the amount of H2 released by each 1 g of employed substrate, the amines have been classified into three classes: poor (1,2,3,4-tetrahydroquinaldine, 2-methylindoline, and 2,6-dimethylpiperidine), moderate (1,2,3,4-tetrahydroquinoline and 6-methyl-1,2,3,4-tetrahydroquinoline), and good hydrogen donors (1,2,3,4-tetrahydroisoquinoline).Financial support from the MINECO of Spain (Projects CTQ2014-52799-P and CTQ2016-81797-REDC), the Diputacion General de Aragón (E-35), FEDER, and the European Social Fund is acknowledged.Peer reviewedAmerican Chemical SocietyDiputación General de AragónMinisterio de Economía y Competitividad (España)European CommissionConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]201720172017info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/154601reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info: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/CTQ2016-81797-REDChttps://doi.org//10.1021/acs.organomet.7b00521Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1546012026-05-22T06:33:51Z
dc.title.none.fl_str_mv Osmium hydride acetylacetonate complexes and their application in acceptorless dehydrogenative coupling of alcohols and amines and for the dehydrogenation of cyclic amines
title Osmium hydride acetylacetonate complexes and their application in acceptorless dehydrogenative coupling of alcohols and amines and for the dehydrogenation of cyclic amines
spellingShingle Osmium hydride acetylacetonate complexes and their application in acceptorless dehydrogenative coupling of alcohols and amines and for the dehydrogenation of cyclic amines
Esteruelas, Miguel A.
title_short Osmium hydride acetylacetonate complexes and their application in acceptorless dehydrogenative coupling of alcohols and amines and for the dehydrogenation of cyclic amines
title_full Osmium hydride acetylacetonate complexes and their application in acceptorless dehydrogenative coupling of alcohols and amines and for the dehydrogenation of cyclic amines
title_fullStr Osmium hydride acetylacetonate complexes and their application in acceptorless dehydrogenative coupling of alcohols and amines and for the dehydrogenation of cyclic amines
title_full_unstemmed Osmium hydride acetylacetonate complexes and their application in acceptorless dehydrogenative coupling of alcohols and amines and for the dehydrogenation of cyclic amines
title_sort Osmium hydride acetylacetonate complexes and their application in acceptorless dehydrogenative coupling of alcohols and amines and for the dehydrogenation of cyclic amines
dc.creator.none.fl_str_mv Esteruelas, Miguel A.
Lezáun, Virginia
Martínez, Antonio
Oliván, Montserrat
Oñate, Enrique
author Esteruelas, Miguel A.
author_facet Esteruelas, Miguel A.
Lezáun, Virginia
Martínez, Antonio
Oliván, Montserrat
Oñate, Enrique
author_role author
author2 Lezáun, Virginia
Martínez, Antonio
Oliván, Montserrat
Oñate, Enrique
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Diputación General de Aragón
Ministerio de Economía y Competitividad (España)
European Commission
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description The preparation of new osmium hydride complexes, starting from OsH6(PiPr3)2 (1) and OsH2Cl2(PiPr3)2 (2), and their catalytic activity in acceptorless dehydrogenative coupling of alcohols and amines and in dehydrogenation of cyclic amines are reported. Complex 1 reacts with acetylacetone (Hacac) to give the classical trihydride OsH3(acac)(PiPr3)2 (3). The protonation of 3 with triflic acid (HOTf) produces the release of H2 and the formation of the unsaturated osmium(IV) dihydride [OsH2(acac)(PiPr3)2]OTf (4), which is also prepared by starting from 2 via the intermediate OsH2Cl(acac)(PiPr3)2 (5). Treatment of an acetylacetone solution of 5 with KOH affords Os(acac)2(PiPr3)2 (6). In the presence of 5 mol % of KOH, complexes 3–6 promote the coupling of benzyl alcohol and aniline to give N-benzylideneaniline and H2. Under the same conditions, complex 3 catalyzes a wide range of analogous couplings to afford a variety of imines, including aliphatic imines, with yields between 90 and 40% after 1–48 h. Complex 3 also catalyzes the dehydrogenation of cyclic amines. According to the amount of H2 released by each 1 g of employed substrate, the amines have been classified into three classes: poor (1,2,3,4-tetrahydroquinaldine, 2-methylindoline, and 2,6-dimethylpiperidine), moderate (1,2,3,4-tetrahydroquinoline and 6-methyl-1,2,3,4-tetrahydroquinoline), and good hydrogen donors (1,2,3,4-tetrahydroisoquinoline).
publishDate 2017
dc.date.none.fl_str_mv 2017
2017
2017
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/154601
url http://hdl.handle.net/10261/154601
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
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/CTQ2016-81797-REDC
https://doi.org//10.1021/acs.organomet.7b00521
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)
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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