Nickel and Palladium Complexes with New Phosphinito-Imine Ligands and Their Application as Ethylene Oligomerization Catalysts

Phosphinito-imines, a new class of P,N donors, are readily generated by reaction of bulky arylamide anions [R2CONAr]− (R2 = Me or t-Bu; Ar = 2,6-i-Pr2C6H4) with chlorophosphines ClP(R1)2. In solution, free phosphinito-imines exist in equilibrium with the corresponding amidophosphine tautomers, conta...

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Autores: Ortiz de la Tabla, Laura, Matas, Inmaculada, Palma, Pilar, Álvarez, Eleuterio, Cámpora, Juan
Tipo de recurso: artículo
Fecha de publicación:2013
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/93420
Acceso en línea:http://hdl.handle.net/10261/93420
Access Level:acceso abierto
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spelling Nickel and Palladium Complexes with New Phosphinito-Imine Ligands and Their Application as Ethylene Oligomerization CatalystsOrtiz de la Tabla, LauraMatas, InmaculadaPalma, PilarÁlvarez, EleuterioCámpora, JuanPhosphinito-imines, a new class of P,N donors, are readily generated by reaction of bulky arylamide anions [R2CONAr]− (R2 = Me or t-Bu; Ar = 2,6-i-Pr2C6H4) with chlorophosphines ClP(R1)2. In solution, free phosphinito-imines exist in equilibrium with the corresponding amidophosphine tautomers, containing a nitrogen-bound P(R1)2 group. However, reacting the tautomer mixtures with metal precursor complexes, such as NiBr2(dme) or PdCl2(cod), selectively affords stable phosphinito-imine complexes MX2(P-N) (M = Ni, Pd) in excellent yields. These complexes are diamagnetic and exhibit square-planar structures in the solid state, but in solution, the Ni derivatives exchange with a small amount of the corresponding high-spin tetrahedral isomers. On treatment with MMAO or DEAC, NiX2(P-N) complexes become active ethylene oligomerization catalysts, affording mainly butenes along with smaller amounts of hexenes and octenes. The activity and the selectivity of these catalysts depend on the structure of the phosphinito-imine ligand and the cocatalyst used. When activated with DEAC, complexes containing the P(i-Pr)2 moiety are extremely active, achieving TOFs over 106 mol C2H4/mol Ni·h and high selectivity for butenesPeer reviewedAmerican Chemical Society201420142013info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501http://hdl.handle.net/10261/93420reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Ingléshttp://dx.doi.org/10.1021/om201088yinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/934202026-05-22T06:33:51Z
dc.title.none.fl_str_mv Nickel and Palladium Complexes with New Phosphinito-Imine Ligands and Their Application as Ethylene Oligomerization Catalysts
title Nickel and Palladium Complexes with New Phosphinito-Imine Ligands and Their Application as Ethylene Oligomerization Catalysts
spellingShingle Nickel and Palladium Complexes with New Phosphinito-Imine Ligands and Their Application as Ethylene Oligomerization Catalysts
Ortiz de la Tabla, Laura
title_short Nickel and Palladium Complexes with New Phosphinito-Imine Ligands and Their Application as Ethylene Oligomerization Catalysts
title_full Nickel and Palladium Complexes with New Phosphinito-Imine Ligands and Their Application as Ethylene Oligomerization Catalysts
title_fullStr Nickel and Palladium Complexes with New Phosphinito-Imine Ligands and Their Application as Ethylene Oligomerization Catalysts
title_full_unstemmed Nickel and Palladium Complexes with New Phosphinito-Imine Ligands and Their Application as Ethylene Oligomerization Catalysts
title_sort Nickel and Palladium Complexes with New Phosphinito-Imine Ligands and Their Application as Ethylene Oligomerization Catalysts
dc.creator.none.fl_str_mv Ortiz de la Tabla, Laura
Matas, Inmaculada
Palma, Pilar
Álvarez, Eleuterio
Cámpora, Juan
author Ortiz de la Tabla, Laura
author_facet Ortiz de la Tabla, Laura
Matas, Inmaculada
Palma, Pilar
Álvarez, Eleuterio
Cámpora, Juan
author_role author
author2 Matas, Inmaculada
Palma, Pilar
Álvarez, Eleuterio
Cámpora, Juan
author2_role author
author
author
author
description Phosphinito-imines, a new class of P,N donors, are readily generated by reaction of bulky arylamide anions [R2CONAr]− (R2 = Me or t-Bu; Ar = 2,6-i-Pr2C6H4) with chlorophosphines ClP(R1)2. In solution, free phosphinito-imines exist in equilibrium with the corresponding amidophosphine tautomers, containing a nitrogen-bound P(R1)2 group. However, reacting the tautomer mixtures with metal precursor complexes, such as NiBr2(dme) or PdCl2(cod), selectively affords stable phosphinito-imine complexes MX2(P-N) (M = Ni, Pd) in excellent yields. These complexes are diamagnetic and exhibit square-planar structures in the solid state, but in solution, the Ni derivatives exchange with a small amount of the corresponding high-spin tetrahedral isomers. On treatment with MMAO or DEAC, NiX2(P-N) complexes become active ethylene oligomerization catalysts, affording mainly butenes along with smaller amounts of hexenes and octenes. The activity and the selectivity of these catalysts depend on the structure of the phosphinito-imine ligand and the cocatalyst used. When activated with DEAC, complexes containing the P(i-Pr)2 moiety are extremely active, achieving TOFs over 106 mol C2H4/mol Ni·h and high selectivity for butenes
publishDate 2013
dc.date.none.fl_str_mv 2013
2014
2014
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/93420
url http://hdl.handle.net/10261/93420
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv http://dx.doi.org/10.1021/om201088y
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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