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

Anthony Kermagoret, Rachel Nathaniel Kerber, Matthew P. Conley, Emmanuel Callens, Pierre Florian, Dominique Massiot, Françoise Delbecq, Xavier Rozanska, Christophe Copéret, Philippe Sautet

Research output: Contribution to journalArticlepeer-review

39 Scopus citations

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.
Original languageEnglish (US)
Pages (from-to)46-54
Number of pages9
JournalJournal of Catalysis
Volume313
DOIs
StatePublished - May 2014
Externally publishedYes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): UK-00017
Acknowledgements: 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.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

Fingerprint

Dive into the research topics of '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'. Together they form a unique fingerprint.

Cite this