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

Vincent Tognetti 1, 2 Antoine Buchard 3 Audrey Auffrant 3 Pascal Le Floch 3 Carlo Adamo 2, * Ilaria Ciofini 2
* Corresponding author
1 COBRA - Chimie Organique et Bioorganique : Réactivité et Analyse
2 LECIME - Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie (LECIME - UMR 7575)
3 DCPH - Laboratoire Hétéroéléments et Coordination
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.
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Journal articles
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https://hal-polytechnique.archives-ouvertes.fr/hal-00906360
Contributor : Francoise Girard <>
Submitted on : Tuesday, November 19, 2013 - 3:52:49 PM
Last modification on : Wednesday, November 27, 2019 - 8:26:05 AM

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Vincent Tognetti, Antoine Buchard, Audrey Auffrant, Pascal Le Floch, Carlo Adamo, et al.. Ethylene dimerization catalyzed by mixed phosphine-iminophosphorane nickel(II) complexes: a DFT investigation. Journal of Molecular Modeling, Springer Verlag (Germany), 2013, 19, pp.2107-2118. ⟨10.1007/s00894-012-1631-9⟩. ⟨hal-00906360⟩

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