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Theoretical Insight into the Effect of Fluorine‐Functionalized Metal‐Organic Framework Supported Palladium Single‐Site Catalyst in the Ethylene Dimerization Reaction
Author(s) -
Ortega Daniela E.
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202101072
Subject(s) - catalysis , palladium , steric effects , chemistry , ligand (biochemistry) , ethylene , catalytic cycle , selectivity , photochemistry , fluorine , combinatorial chemistry , surface modification , metal organic framework , organic chemistry , adsorption , biochemistry , receptor
Ethylene dimerization reaction is one of the most common mechanisms for the production of 1‐butene. Recently, metal–organic frameworks (MOFs) have received extensive attention in this area since they combine all the advantages of homogeneous and heterogeneous catalysts in a single compound. Here a computational mechanistic study of MOF‐supported palladium single‐site catalyst for ethylene dimerization reaction is reported. Catalytic systems with both biphenyl‐type backbone as organic ligand and its fluorine‐functionalization have been investigated to reveal the origin of ligand effects on the catalytic activity and selectivity. The calculations revealed that the nonfluorinated palladium MOF catalyst undergoes dimerization over isomerization reaction. Then the influence of the fluorine‐functionalized organic ligand was compared in the dimerization catalytic cycle, which was strongly favored in terms of activity and selectivity. Catalyst‐substrate interactions were analyzed by energy decomposition analysis revealing the critical role of ligand backbone functionalization on the activity. This theoretical analysis identified three chemically meaningful dominant effects on these catalysts; steric, electrostatic and charge transfer effects. The steric effects promote nonfluorinated MOF catalyst, whereas the electrostatic effects are the dominant factor that promotes its fluorinated counterpart. This theoretical study provides feedback with future experimental studies about the role of fluorine ligand functionalization in palladium MOF catalysts for ethylene dimerization reaction.