Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanes

Enantiopure P-stereogenic methylphosphane-boranes (SP)-P(BH3)PhArMe (ArMe; Ar = 1-naphthyl (NpMe), and 2-biphenylyl (BiphMe)) have been used to prepare diphosphanes of the type ArPhPCH2PR2 (R = Ph, iPr or tBu; ArR). The ligands have been reacted with [Rh(COD)2]BF4 to furnish the corresponding six mo...

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Autores: Eusamio, Javier, Medina, Yaiza M., Córdoba, Javier C., Vidal Ferran, Anton, Sainz García, Daniel, Gutiérrez, Albert, Font Bardia, Ma. Mercedes, Grabulosa, Arnald
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Recursos:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/217084
Acesso em linha:https://hdl.handle.net/2445/217084
Access Level:acceso abierto
Palavra-chave:Rodi
Ruteni
Compostos organometàl·lics
Rhodium
Ruthenium
Organometallic compounds
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spelling Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanesEusamio, JavierMedina, Yaiza M.Córdoba, Javier C.Vidal Ferran, AntonSainz García, DanielGutiérrez, AlbertFont Bardia, Ma. MercedesGrabulosa, ArnaldRodiRuteniCompostos organometàl·licsRhodiumRutheniumOrganometallic compoundsEnantiopure P-stereogenic methylphosphane-boranes (SP)-P(BH3)PhArMe (ArMe; Ar = 1-naphthyl (NpMe), and 2-biphenylyl (BiphMe)) have been used to prepare diphosphanes of the type ArPhPCH2PR2 (R = Ph, iPr or tBu; ArR). The ligands have been reacted with [Rh(COD)2]BF4 to furnish the corresponding six monochelated [Rh(COD)(ArR)]BF4 organometallic compounds (RhArR) or, depending on the reaction conditions, the bis(chelated) coordination compound [Rh(BiphiPr)2]BF4 as a mixture of cis and trans isomers. The crystal structure of cis-[Rh(BiphiPr)2]BF4 was obtained. The coordination of the BiphR with [RuCl(μ-Cl)(η6-p-cymene)2]2 under different conditions produced cationic chelated complexes of the type [RuCl(η6-p-cymene)(κ2-BiphR)]PF6 (RuBiphR) and the neutral monocoordinated complex [RuCl2(η6- p-cymene)(κ1-BiphPh)] (RuBiphPh') with the uncoordinated P-stereogenic moiety. The Rh(I) complexes were used in the catalytic hydrogenation of functionalized olefins and the Ru(II) complexes were tested in the transfer hydrogenation of acetophenone. Both precursors displayed good activities with moderate enantioselectivities.Royal Society of Chemistry2023info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://hdl.handle.net/2445/217084Articles publicats en revistes (Química Inorgànica i Orgànica)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésReproducció del document publicat a: https://doi.org/10.1039/D2DT04026CDalton Transactions, 2023, vol. 52, p. 2424-2439cc-by (c) Eusamio, J. et al., 2023http://creativecommons.org/licenses/by/3.0/es/info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/2170842026-05-27T06:46:51Z
dc.title.none.fl_str_mv Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanes
title Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanes
spellingShingle Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanes
Eusamio, Javier
Rodi
Ruteni
Compostos organometàl·lics
Rhodium
Ruthenium
Organometallic compounds
title_short Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanes
title_full Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanes
title_fullStr Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanes
title_full_unstemmed Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanes
title_sort Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanes
dc.creator.none.fl_str_mv Eusamio, Javier
Medina, Yaiza M.
Córdoba, Javier C.
Vidal Ferran, Anton
Sainz García, Daniel
Gutiérrez, Albert
Font Bardia, Ma. Mercedes
Grabulosa, Arnald
author Eusamio, Javier
author_facet Eusamio, Javier
Medina, Yaiza M.
Córdoba, Javier C.
Vidal Ferran, Anton
Sainz García, Daniel
Gutiérrez, Albert
Font Bardia, Ma. Mercedes
Grabulosa, Arnald
author_role author
author2 Medina, Yaiza M.
Córdoba, Javier C.
Vidal Ferran, Anton
Sainz García, Daniel
Gutiérrez, Albert
Font Bardia, Ma. Mercedes
Grabulosa, Arnald
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Rodi
Ruteni
Compostos organometàl·lics
Rhodium
Ruthenium
Organometallic compounds
topic Rodi
Ruteni
Compostos organometàl·lics
Rhodium
Ruthenium
Organometallic compounds
description Enantiopure P-stereogenic methylphosphane-boranes (SP)-P(BH3)PhArMe (ArMe; Ar = 1-naphthyl (NpMe), and 2-biphenylyl (BiphMe)) have been used to prepare diphosphanes of the type ArPhPCH2PR2 (R = Ph, iPr or tBu; ArR). The ligands have been reacted with [Rh(COD)2]BF4 to furnish the corresponding six monochelated [Rh(COD)(ArR)]BF4 organometallic compounds (RhArR) or, depending on the reaction conditions, the bis(chelated) coordination compound [Rh(BiphiPr)2]BF4 as a mixture of cis and trans isomers. The crystal structure of cis-[Rh(BiphiPr)2]BF4 was obtained. The coordination of the BiphR with [RuCl(μ-Cl)(η6-p-cymene)2]2 under different conditions produced cationic chelated complexes of the type [RuCl(η6-p-cymene)(κ2-BiphR)]PF6 (RuBiphR) and the neutral monocoordinated complex [RuCl2(η6- p-cymene)(κ1-BiphPh)] (RuBiphPh') with the uncoordinated P-stereogenic moiety. The Rh(I) complexes were used in the catalytic hydrogenation of functionalized olefins and the Ru(II) complexes were tested in the transfer hydrogenation of acetophenone. Both precursors displayed good activities with moderate enantioselectivities.
publishDate 2023
dc.date.none.fl_str_mv 2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/217084
url https://hdl.handle.net/2445/217084
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Reproducció del document publicat a: https://doi.org/10.1039/D2DT04026C
Dalton Transactions, 2023, vol. 52, p. 2424-2439
dc.rights.none.fl_str_mv cc-by (c) Eusamio, J. et al., 2023
http://creativecommons.org/licenses/by/3.0/es/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv cc-by (c) Eusamio, J. et al., 2023
http://creativecommons.org/licenses/by/3.0/es/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv Articles publicats en revistes (Química Inorgànica i Orgànica)
reponame:Dipòsit Digital de la UB
instname:Universidad de Barcelona
instname_str Universidad de Barcelona
reponame_str Dipòsit Digital de la UB
collection Dipòsit Digital de la UB
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,812429

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