title: Ethylene dimerization catalyzed by mixed phosphine-iminophosphorane nickel(II) complexes: a DFT investigation.
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.
authors.affiliation: Laboratoire 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.
authors.forename: Vincent
authors.initials: V
authors.lastname: Tognetti
authors.forename: Antoine
authors.initials: A
authors.lastname: Buchard
authors.forename: Audrey
authors.initials: A
authors.lastname: Auffrant
authors.forename: Ilaria
authors.initials: I
authors.lastname: Ciofini
authors.forename: Pascal
authors.initials: P
authors.lastname: Le Floch
authors.forename: Carlo
authors.initials: C
authors.lastname: Adamo