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Updated: May 16, 2026

Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
Published on: November 27, 2015
Ethylene dimerization catalyzed by mixed phosphine-iminophosphorane nickel(II) complexes: a DFT investigation
Vincent Tognetti1, Antoine Buchard, Audrey Auffrant
1Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie, LECIME CNRS UMR-7575, Ecole Nationale Supérieure de Chimie de Paris-Chimie ParisTech, 11 rue Pierre et Marie Curie, Paris Cedex 05, Paris, France.
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 asymmetry 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.
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