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 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.
Document type :
Journal articles
Complete list of metadatas

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

Links full text

Identifiers

Citation

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⟩

Share

Metrics

Record views

402