TY - JOUR
T1 - Ethylene dimerization catalyzed by mixed phosphine–iminophosphorane nickel(II) complexes: a DFT investigation
AU - Tognetti, Vincent
AU - Buchard, Antoine
AU - Auffrant, Audrey
AU - Ciofini, Ilaria
AU - Le Floch, Pascal
AU - Adamo, Carlo
PY - 2013
Y1 - 2013
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84869871921&partnerID=8YFLogxK
UR - http://dx.doi.org/10.1007/s00894-012-1631-9
U2 - 10.1007/s00894-012-1631-9
DO - 10.1007/s00894-012-1631-9
M3 - Article
SN - 1610-2940
VL - 19
SP - 2107
EP - 2118
JO - Journal of Molecular Modeling
JF - Journal of Molecular Modeling
IS - 5
ER -