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Updated: May 26, 2026

A Protocol for Safe Lithiation Reactions Using Organolithium Reagents
Published on: November 12, 2016
Ion pair pKs of some amines: extension of the computed lithium pK scale
Andrew Streitwieser1, Antonio Facchetti, Linfeng Xie
1Department of Chemistry, University of California-Berkeley, Berkeley, California 94720-1460, USA. astreit@berkeley.edu
Abstract:
The pK of p-(methylamino)biphenyl, 1, on our Li scale, pK(Li) = 22.09, compared to the cesium scale, pK(Cs) = 28.60. For hexamethyldisilazane, HMDS, pK(Li) = 23.05, pK(Cs) = 29.26. These results are those for the monomers in THF; corrections were made for dimers present in some cases. The pK(Li) of these two amines fit well the previously found correlation with Hartree-Fock calculations at 6-31+g(d) using RLi coordinated with three dimethyl ethers as a computational model for RLi in THF. The results are also compared with earlier pK(Li)s reported from equilibria with lithium amides in which aggregation was not considered.
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