Why Can Cationic Halogen Bond Donors Activate the Ritter-Type Solvolysis of Benzhydryl Bromide but Cationic Hydrogen Bond Donors Can Not?
Yueyan Wang, Peifeng Su
Abstract
, were explored theoretically. Our study revealed that the activation difference can be contributed by the variation of the noncovalent interactions. For halogen bond donors, the successful activation is attributed by halogen bond and lone pair···π. The halogen bonds mainly provide the stabilization energy of the ion-pair complex with the help of lone pair···π. For hydrogen-bond donors, the contribution of the hydrogen bond is unable to compensate the like-charge repulsion arising from the generation of the carbocation, leading to the unsuccessful activation. In general, lone pair···π makes a difference.
Topics & Concepts
Cationic polymerizationChemistrySolvolysisBromideHalogen bondMedicinal chemistryHydrogen bondHalogenPolymer chemistryOrganic chemistryMoleculeHydrolysisAlkylCrystallography and molecular interactionsChemical Thermodynamics and Molecular StructureAdvanced Chemical Physics Studies