Chlorodiethylaluminum supported on silica: A dinuclear aluminum surface species with bridging μ2-Cl-ligand as a highly efficient co-catalyst for the Ni-catalyzed dimerization of ethene

Handle URI:
http://hdl.handle.net/10754/597776
Title:
Chlorodiethylaluminum supported on silica: A dinuclear aluminum surface species with bridging μ2-Cl-ligand as a highly efficient co-catalyst for the Ni-catalyzed dimerization of ethene
Authors:
Kermagoret, Anthony; Kerber, Rachel Nathaniel; Conley, Matthew P.; Callens, Emmanuel; Florian, Pierre; Massiot, Dominique; Delbecq, Françoise; Rozanska, Xavier; Copéret, Christophe; Sautet, Philippe
Abstract:
Silica-supported chloro alkyl aluminum co-catalysts (DEAC@support) were prepared via Surface Organometallic Chemistry by contacting diethylaluminum chloride (DEAC) and high specific surface silica materials, i.e. SBA-15, MCM-41, and Aerosil SiO2. Such systems efficiently activate NiCl 2(PBu3)2 for catalytic ethene dimerization, with turnover frequency (TOF) reaching up to 498,000 molC2H4/ (molNi h) for DEAC@MCM-41. A detailed analysis of the DEAC@SBA-15 co-catalyst structure by solid-state aluminum-27 NMR at high-field (17.6 T and 20.0 T) and ultrafast spinning rates allows to detect six sites, characterized by a distribution of quadrupolar interaction principal values CQ and isotropic chemical shifts δiso. Identification of the corresponding Al-grafted structures was possible by comparison of the experimental NMR signatures with these calculated by DFT on a wide range of models for the aluminum species (mono- versus di-nuclear, mono- versus bis-grafted with bridging Cl or ethyl). Most of the sites were identified as dinuclear species with retention of the structure of DEAC, namely with the presence of μ2-Cl-ligands between two aluminum, and this probably explains the high catalytic performance of this silica-supported co-catalysts. © 2014 Elsevier Inc. All rights reserved.
Citation:
Kermagoret A, Kerber RN, Conley MP, Callens E, Florian P, et al. (2014) Chlorodiethylaluminum supported on silica: A dinuclear aluminum surface species with bridging μ2-Cl-ligand as a highly efficient co-catalyst for the Ni-catalyzed dimerization of ethene. Journal of Catalysis 313: 46–54. Available: http://dx.doi.org/10.1016/j.jcat.2014.02.006.
Publisher:
Elsevier BV
Journal:
Journal of Catalysis
KAUST Grant Number:
UK-00017
Issue Date:
May-2014
DOI:
10.1016/j.jcat.2014.02.006
Type:
Article
ISSN:
0021-9517
Sponsors:
This publication is based on work supported by Award No.UK-00017, made by King Abdullah University of Science and Technology (KAUST), and by the TGE RMN THC Fr3050. The authors thank the PSMN at ENS of Lyon for the attribution of CPU time.
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Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorKermagoret, Anthonyen
dc.contributor.authorKerber, Rachel Nathanielen
dc.contributor.authorConley, Matthew P.en
dc.contributor.authorCallens, Emmanuelen
dc.contributor.authorFlorian, Pierreen
dc.contributor.authorMassiot, Dominiqueen
dc.contributor.authorDelbecq, Françoiseen
dc.contributor.authorRozanska, Xavieren
dc.contributor.authorCopéret, Christopheen
dc.contributor.authorSautet, Philippeen
dc.date.accessioned2016-02-25T12:56:31Zen
dc.date.available2016-02-25T12:56:31Zen
dc.date.issued2014-05en
dc.identifier.citationKermagoret A, Kerber RN, Conley MP, Callens E, Florian P, et al. (2014) Chlorodiethylaluminum supported on silica: A dinuclear aluminum surface species with bridging μ2-Cl-ligand as a highly efficient co-catalyst for the Ni-catalyzed dimerization of ethene. Journal of Catalysis 313: 46–54. Available: http://dx.doi.org/10.1016/j.jcat.2014.02.006.en
dc.identifier.issn0021-9517en
dc.identifier.doi10.1016/j.jcat.2014.02.006en
dc.identifier.urihttp://hdl.handle.net/10754/597776en
dc.description.abstractSilica-supported chloro alkyl aluminum co-catalysts (DEAC@support) were prepared via Surface Organometallic Chemistry by contacting diethylaluminum chloride (DEAC) and high specific surface silica materials, i.e. SBA-15, MCM-41, and Aerosil SiO2. Such systems efficiently activate NiCl 2(PBu3)2 for catalytic ethene dimerization, with turnover frequency (TOF) reaching up to 498,000 molC2H4/ (molNi h) for DEAC@MCM-41. A detailed analysis of the DEAC@SBA-15 co-catalyst structure by solid-state aluminum-27 NMR at high-field (17.6 T and 20.0 T) and ultrafast spinning rates allows to detect six sites, characterized by a distribution of quadrupolar interaction principal values CQ and isotropic chemical shifts δiso. Identification of the corresponding Al-grafted structures was possible by comparison of the experimental NMR signatures with these calculated by DFT on a wide range of models for the aluminum species (mono- versus di-nuclear, mono- versus bis-grafted with bridging Cl or ethyl). Most of the sites were identified as dinuclear species with retention of the structure of DEAC, namely with the presence of μ2-Cl-ligands between two aluminum, and this probably explains the high catalytic performance of this silica-supported co-catalysts. © 2014 Elsevier Inc. All rights reserved.en
dc.description.sponsorshipThis publication is based on work supported by Award No.UK-00017, made by King Abdullah University of Science and Technology (KAUST), and by the TGE RMN THC Fr3050. The authors thank the PSMN at ENS of Lyon for the attribution of CPU time.en
dc.publisherElsevier BVen
dc.subjectAluminum-27 solid state NMRen
dc.subjectChloroalkylaluminumen
dc.subjectCo-catalystsen
dc.subjectDFT calculationsen
dc.subjectDimerization of etheneen
dc.subjectHeterogeneous catalystsen
dc.subjectNickelen
dc.subjectOligomerizationen
dc.subjectSilica supporteden
dc.titleChlorodiethylaluminum supported on silica: A dinuclear aluminum surface species with bridging μ2-Cl-ligand as a highly efficient co-catalyst for the Ni-catalyzed dimerization of etheneen
dc.typeArticleen
dc.identifier.journalJournal of Catalysisen
dc.contributor.institutionUniversite Claude Bernard Lyon 1, Villeurbanne, Franceen
dc.contributor.institutionUniversite de Lyon, Lyon, Franceen
dc.contributor.institutionEidgenossische Technische Hochschule Zurich, Zurich, Switzerlanden
dc.contributor.institutionUniversite d'Orleans, Orleans, Franceen
kaust.grant.numberUK-00017en
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