Lithium cation basicity: revisiting the high basicity range by experiment and theory

摘要

A Lithium cation basicitie (LiCB) scale is established between tetrahydrofuran (137.4 kJ mol~(-1)) and the enol of the acetylacetone (203.2 kJ mol~(-1)) for a series of (30) compounds by mean of equilibriummeasurements using FTICR. The direct equilibrium measurement of ΔLiCBs can be achieved in spite of the Li~+-bound dimers formation: the feasibility of equilibriummeasurements was provedby themeans of a kinetic model. Furthermore, a correlation with a slope close to unity between our LiCB measurements and the previous ones (reviewby Laurence and Gal [1]) was observed in lower part of the scale. These new measurements are in good agreement with calculations at the G2MP2 level (MAD = 1.8 kJ mol~(-1)).