Ligand Exchange Processes on Solvated Lithium Cations: Complexation by Cryptands in Acetone as Solvent

Abstract

Kinetic studies on Li + exchange between the cryptands C222 and C221 and acetone as solvent were performed as a function of ligand-to-metal ratio, temperature and pressure using 7 Li NMR spectroscopy. Temperature and pressure dependence measurements were performed in the presence of an excess of Li + . The rate and activation parameters for the exchange process are: C222: k 298 = (1.7Ϯ 0.

Application of High Pressure in the Elucidation of Inorganic and Bioinorganic Reaction Mechanisms

“…[381][382][383][384] A parallel study with the same cryptands and using acetone as a solvent species for Li þ ions also demonstrated little pressure dependence of the kinetics of exchange between cryptand and acetone, although the entropy of activation suggested an associative interchange mechanism. 385 DFT calculations examined the consequence of the cryptand cavity size in relation to kinetic parameters.…”