Journal
CHEMPHYSCHEM
Volume 24, Issue 1, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.202200634
Keywords
Lewis acids; hypervalent iodine; halogen bonding; energy decomposition analysis; iodonium
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This study analyzes and explains the higher Lewis acidity of cyclic diaryliodonium compounds using quantum-chemical calculations and energy decomposition analyses. The change in energy levels and hybridization of iodine's orbitals is the key factor leading to the increased Lewis acidity, resulting in more favorable electrostatic interaction and better charge transfer.
Cyclic diaryliodonium compounds like iodolium derivatives have increasingly found use as noncovalent Lewis acids in the last years. They are more stable toward nucleophilic substitution than acyclic systems and are markedly more Lewis acidic. Herein, this higher Lewis acidity is analyzed and explained via quantum-chemical calculations and energy decomposition analyses. Its key origin is the change in energy levels and hybridization of iodine's orbitals, leading to both more favorable electrostatic interaction and better charge transfer. Both of the latter seem to contribute in similar fashion, while hydrogen bonding as well as steric repulsion with the phenyl rings play at best a minor role. In comparison to iodolium, bromolium and chlorolium are less Lewis acidic the lighter the halogen, which is predominantly based on less favorable charge-transfer interactions.
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