β-Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands.

Nickel and palladium methoxides [((iPr)PCP)M-OMe], which contain the (iPr)PCP pincer ligand, decompose upon heating to give products of different kinds. The palladium derivative cleanly gives the dimeric Pd(0) complex [Pd(μ-(iPr)PCHP)]2 ((iPr)PCHP = 2,6-bis(diisopropylphosphinomethyl)phenyl) and for...

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Autores: Martínez-Prieto, Luis Miguel, Ávila, Elena, Palma, Pilar, Álvarez, Eleuterio, Cámpora, Juan
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2015
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/121512
Acceso en línea:http://hdl.handle.net/10261/121512
Access Level:acceso abierto
Palabra clave:Alcohol oxidation
Alkoxides
Dehydrogenation
Pincer ligands
Reaction mechanisms
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spelling β-Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands.Martínez-Prieto, Luis MiguelÁvila, ElenaPalma, PilarÁlvarez, EleuterioCámpora, JuanAlcohol oxidationAlkoxidesDehydrogenationPincer ligandsReaction mechanismsNickel and palladium methoxides [((iPr)PCP)M-OMe], which contain the (iPr)PCP pincer ligand, decompose upon heating to give products of different kinds. The palladium derivative cleanly gives the dimeric Pd(0) complex [Pd(μ-(iPr)PCHP)]2 ((iPr)PCHP = 2,6-bis(diisopropylphosphinomethyl)phenyl) and formaldehyde. In contrast, decomposition of [((iPr)PCP)Ni-OMe] affords polynuclear carbonyl phosphine complexes. Both decomposition processes are initiated by β-hydrogen elimination (BHE), but the resulting [((iPr)PCP)M-H] hydrides undergo divergent reaction sequences that ultimately lead to the irreversible breakdown of the pincer units. Whereas the Pd hydride spontaneously experiences reductive C-H coupling, the decay of its Ni analogue is brought about by its reaction with formaldehyde released in the BHE step. Kinetic measurements showed that the BHE reaction is reversible and less favourable for Ni than for Pd for both kinetic and thermodynamic reasons. DFT calculations confirmed the main conclusions of the kinetic studies and provided further insight into the mechanisms of the decomposition reactions.Peer reviewedJohn Wiley & SonsConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2015info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/121512reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Ingléshttp://dx.doi.org/10.1002/chem.201500652Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1215122026-05-22T06:33:51Z
dc.title.none.fl_str_mv β-Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands.
title β-Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands.
spellingShingle β-Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands.
Martínez-Prieto, Luis Miguel
Alcohol oxidation
Alkoxides
Dehydrogenation
Pincer ligands
Reaction mechanisms
title_short β-Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands.
title_full β-Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands.
title_fullStr β-Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands.
title_full_unstemmed β-Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands.
title_sort β-Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands.
dc.creator.none.fl_str_mv Martínez-Prieto, Luis Miguel
Ávila, Elena
Palma, Pilar
Álvarez, Eleuterio
Cámpora, Juan
author Martínez-Prieto, Luis Miguel
author_facet Martínez-Prieto, Luis Miguel
Ávila, Elena
Palma, Pilar
Álvarez, Eleuterio
Cámpora, Juan
author_role author
author2 Ávila, Elena
Palma, Pilar
Álvarez, Eleuterio
Cámpora, Juan
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Alcohol oxidation
Alkoxides
Dehydrogenation
Pincer ligands
Reaction mechanisms
topic Alcohol oxidation
Alkoxides
Dehydrogenation
Pincer ligands
Reaction mechanisms
description Nickel and palladium methoxides [((iPr)PCP)M-OMe], which contain the (iPr)PCP pincer ligand, decompose upon heating to give products of different kinds. The palladium derivative cleanly gives the dimeric Pd(0) complex [Pd(μ-(iPr)PCHP)]2 ((iPr)PCHP = 2,6-bis(diisopropylphosphinomethyl)phenyl) and formaldehyde. In contrast, decomposition of [((iPr)PCP)Ni-OMe] affords polynuclear carbonyl phosphine complexes. Both decomposition processes are initiated by β-hydrogen elimination (BHE), but the resulting [((iPr)PCP)M-H] hydrides undergo divergent reaction sequences that ultimately lead to the irreversible breakdown of the pincer units. Whereas the Pd hydride spontaneously experiences reductive C-H coupling, the decay of its Ni analogue is brought about by its reaction with formaldehyde released in the BHE step. Kinetic measurements showed that the BHE reaction is reversible and less favourable for Ni than for Pd for both kinetic and thermodynamic reasons. DFT calculations confirmed the main conclusions of the kinetic studies and provided further insight into the mechanisms of the decomposition reactions.
publishDate 2015
dc.date.none.fl_str_mv 2015
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/10261/121512
url http://hdl.handle.net/10261/121512
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv http://dx.doi.org/10.1002/chem.201500652
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv John Wiley & Sons
publisher.none.fl_str_mv John Wiley & Sons
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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score 15,81155

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