Unraveling the role of entropy in tuning unimolecular vs . bimolecular reaction rates: The case of olefin polymerization catalyzed by transition metals

Laura Falivene, Vincenzo Barone, Giovanni Talarico

Research output: Contribution to journalArticlepeer-review

29 Scopus citations

Abstract

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.
Original languageEnglish (US)
Pages (from-to)138-144
Number of pages7
JournalMolecular Catalysis
Volume452
DOIs
StatePublished - Apr 24 2018

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