Ethylene dimerization catalyzed by mixed phosphine–iminophosphorane nickel(II) complexes: a DFT investigation

Vincent Tognetti, Antoine Buchard, Audrey Auffrant, Ilaria Ciofini, Pascal Le Floch, Carlo Adamo

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

A computational study utilizing density functional theory (DFT) was performed to analyze the mechanism of ethylene dimerization catalyzed by (P,N) nickel(II) complexes, where (P,N) is a mixed phosphine–iminophosphorane ligand. Two plausible reaction pathways were considered, namely the Cossee and metallacycle pathways, for three model systems. The fundamental role of ligand assymetry and the importance of steric and trans effects were elucidated. In order to discriminate between both mechanisms, the activation of the precatalyst by trimethylaluminum was modeled. The results obtained allow the establishment of useful guidelines for creating new specifically tailored nickel-based catalysts for controlled dimerization.
Original languageEnglish
Pages (from-to)2107-2118
JournalJournal of Molecular Modeling
Volume19
Issue number5
Early online date1 Nov 2012
DOIs
Publication statusPublished - 2013

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phosphine
Dimerization
dimerization
Nickel
phosphines
Density functional theory
Ethylene
ethylene
nickel
density functional theory
Ligands
ligands
Chemical activation
activation
catalysts
Catalysts

Cite this

Ethylene dimerization catalyzed by mixed phosphine–iminophosphorane nickel(II) complexes: a DFT investigation. / Tognetti, Vincent; Buchard, Antoine; Auffrant, Audrey; Ciofini, Ilaria; Le Floch, Pascal; Adamo, Carlo.

In: Journal of Molecular Modeling, Vol. 19, No. 5, 2013, p. 2107-2118.

Research output: Contribution to journalArticle

Tognetti, Vincent ; Buchard, Antoine ; Auffrant, Audrey ; Ciofini, Ilaria ; Le Floch, Pascal ; Adamo, Carlo. / Ethylene dimerization catalyzed by mixed phosphine–iminophosphorane nickel(II) complexes: a DFT investigation. In: Journal of Molecular Modeling. 2013 ; Vol. 19, No. 5. pp. 2107-2118.
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