How the choice of a computational model could rule the chemical interpretation: The Ni(II) catalyzed ethylene dimerization as a case study
✍ Scribed by Vincent Tognetti; Pascal Le Floch; Carlo Adamo
- Book ID
- 102305684
- Publisher
- John Wiley and Sons
- Year
- 2009
- Tongue
- English
- Weight
- 355 KB
- Volume
- 31
- Category
- Article
- ISSN
- 0192-8651
No coin nor oath required. For personal study only.
✦ Synopsis
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. © 2009 Wiley Periodicals, Inc. J Comput Chem 2010