Hydroxide Chemoselectivity Changes with Water Microsolvation

Sapir Willdorf-Cohen, Alexander Kaushansky, Dario R. Dekel, Charles E. Diesendruck

Research output: Contribution to journalArticlepeer-review

Abstract

Solvent molecules are known to affect chemical reactions, especially if they interact with one or more of the reactants or catalysts. In ion microsolvation, i.e., solvent molecules in the first solvation sphere, strong electronic interactions are created, leading to significant changes in charge distribution and consequently on their nucleophilicity/electrophilicity and acidity/basicity. Despite a long history of research in the field, fundamental issues regarding the effects of ion microsolvation are still open, especially in the condensed phase. Using reactions between hydroxide and relatively stable quaternary ammonium salts as an example, we show that water microsolvation can change hydroxide's chemoselectivity by differently affecting its basicity and nucleophilicity. In this example, the hydroxide reactivity as a nucleophile is less affected by water microsolvation than its reactivity as a base. These disparities are discussed by calculating and comparing oxidation potentials and polarizabilities of the different water-hydroxide clusters.

Original languageAmerican English
Pages (from-to)10216-10221
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume13
Issue number43
DOIs
StatePublished - 3 Nov 2022

All Science Journal Classification (ASJC) codes

  • General Materials Science
  • Physical and Theoretical Chemistry

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