How the choice of a computational model could rule the chemical interpretation: The Ni(II) catalyzed ethylene dimerization as a case study

Abstract

In this article, we present a critical study of the theoretical protocol used for the determination of the nickel(II) catalyzed ethylene dimerization mechanism, considered as a representative example of the various problems related to the modeling a catalytic cycle. The choice of an appropriate computational procedure is indeed crucial for the validity of the conclusions that will be drawn from the computational process. The influence of the exchange-correlation functional on energetic profiles and geometries, the role of the basis set describing the metal atom, as well as the importance of the chosen molecular model, have been thus examined in details. From the obtained results, some general conclusions and guidelines are presented, which could constitute useful warnings in modeling homogenous catalysis. Besides, the database constituted by our high-level calculations can be used within benchmarking procedures to assess the performances of new computational methods based on density functional theory.

Nickel Catalyzed Olefin Oligomerization and Dimerization

“…Adamo et al carried out an extensive study on the exchange-correlation function, basis set, and model size for the Cossee-Arlman mechanism. 467 In the case of cationic phosphino-iminophosphorane-based nickel catalysts, they concluded that this latest parameter is crucial and it impacts the energy calculations and chemical interpretation tremendously. Moreover, they reported their attempt to link molecular descriptors to the prediction of selective ethylene dimerization catalysts by comparing the ΔG of the ethylene insertion and butene elimination steps, on the butyl intermediates.…”

“…Development of a critical DFT model is paramount for a better understanding and even predictive ambitions. Adamo et al carried out an extensive study on the exchange-correlation function, basis set, and model size for the Cossee-Arlman mechanism . In the case of cationic phosphino-iminophosphorane-based nickel catalysts, they concluded that this latest parameter is crucial and it impacts the energy calculations and chemical interpretation tremendously.…”

The Pivotal Role of Catalysis in France: Selected Examples of Recent Advances and Future Prospects.

“…However, the lack of thermal stability and short lifetimes of homogeneous iron‐based catalysts likely hinder their industrial development . Interesting results for the nickel‐catalyzed selective 1‐butene production from ethylene have been reported, although the mechanistic details are still under discussion . Heterogeneous Ni‐based active catalysts for ethylene oligomerization, such as Ni‐AlSiO 2 mesoporous catalyst (Si/Al=6.5, 2.0 % Ni) using mesoporous non‐ordered silica as a support at 150 °C, have also been reported.…”

Ligand-Induced Product Switching between 4-Methyl-1-pentene and 2-Methyl-1-pentene in Bis(imino)pyridine/V(III)-Catalyzed Propylene Dimerization: Cossee–Arlman Versus Metallacycle Mechanism

“…Despite that the propylene dimerization catalyst is industrially important, the mechanism for propylene dimerization is not well established. In homogeneous catalysis, the mechanism of alkene oligomerization has been extensively investigated. ,− Some theoretical studies on olefin oligomerization based on Ni metal have been investigated, in particular with a detailed comparison of the Cossee–Arlman mechanism and metallacycle mechanism. ,− …”