The original Grunwald-Winstein equation (1948) involved the development of a scale of solvent ionizing power (Y). Subsequent work has refined this scale and involved the development of scales of solvent nucleophilicity (N) and a term to correct for deviations when aromatic rings are present, governed by the aromatic ring parameter (I). These three scales, and the sensitivities towards each, can be related to specific rates of solvolysis through linear free energy relationships (LFERs).
One important area of application of LFERs has been to the solvolyses of tert-alkyl halides. It has been proposed that the solvolysis of tert-butyl chloride involves a nucleophilic component, although other workers have suggested that the effects observed are related to electrophilic not nucleophilic influences. Takeuchi (1997) studied a compound with two of the methyl groups of tert-butyl chloride replaced by neopentyl groups. For this highly-hindered substrate there was no evidence for nucleophilic participation. Liu (1998) and Takeuchi (2001) have reported concerning the solvolyses of additional significantly-hindered tertiary alkyl chlorides. Liu (2009) has presented a parallel study of bromides. Martins (2008) has considered hindered tertiary alkyl halides, mainly with carbon-carbon multiple bonds as substituents. It was proposed that the hI term was of importance, with the sensitivities (h) sometimes positive and sometimes negative. To explain negative values, it was suggested that the I scale might contain a nucleophilicity component. In this review, we bring together, with analysis and commentary, the work of Takeuchi, Liu, Martins and others concerning the solvolyses of tertiary alkyl halides, with emphasis on the relevance of the three scales that have been developed for use in Grunwald-Winstein correlations.