Unraveling the role of entropy in tuning unimolecular vs . bimolecular reaction rates: The case of olefin polymerization catalyzed by transition metals
Type
ArticleKAUST Grant Number
KAUST-2017-C0854Date
2018-04-24Online Publication Date
2018-04-24Print Publication Date
2018-06Permanent link to this record
http://hdl.handle.net/10754/627871
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Show full item recordAbstract
Olefin polymerization catalyzed by Group 4 transition metals is studied here as test case to reveal the entropy effects when bimolecular and unimolecular reactions are computed for processes occurring in solution. Catalytic systems characterized by different ligand frameworks, metal, and growing polymeric chain for which experimental data are available have been selected in order to validate the main approaches to entropy calculation. Applying the “standard” protocol results in a strong disagreement with the experimental results and the methods introducing a direct correction of the translational entropy term based on a single experimental parameter emerge as the most reliable. The general and powerful computational tool achieved in this study can represent a further step towards the “catalyst design” to control and predict the molecular mass of the resulting polymers.Citation
Falivene L, Barone V, Talarico G (2018) Unraveling the role of entropy in tuning unimolecular vs . bimolecular reaction rates: The case of olefin polymerization catalyzed by transition metals. Molecular Catalysis 452: 138–144. Available: http://dx.doi.org/10.1016/j.mcat.2018.04.012.Sponsors
Funding sources from the University of Naples Federico II (Ricerca Ateneo DR_409_2017). G.T. thanks the Kaust Catalysis Center of King Abdullah University of Science and Technology, Thuwal, Saudi Arabia, for the visiting contract KAUST-2017-C0854.Publisher
Elsevier BVJournal
Molecular CatalysisAdditional Links
http://www.sciencedirect.com/science/article/pii/S2468823118301433ae974a485f413a2113503eed53cd6c53
10.1016/j.mcat.2018.04.012