Experimental validation of Gaussian‐3 lithium cation affinities of amides: implications for the gas‐phase lithium cation basicity scale

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Abstract
Using a refined Gaussian‐3 (G3) protocol, the highest level of ab initio calculations reported so far, we have established the Li+ cation binding enthalpy (affinity) at 0 K (in kJ mol−1) for formamide (195.7), N‐methylformamide (209.2), N,N′‐dimethylformamide (220.0), acetamide (211.7), N‐methylacetamide (222.5), and N,N′‐dimethylacetamide (230.1), with an estimated maximum uncertainty of ±8 kJ mol−1. With these six theoretical lithium cation binding affinities as reference values, the absolute Li+ affinities of imidazole and dimethoxyethane were determined by the extended kinetic method, and by adopting the statistical data treatment protocol recently proposed by Armentrout. The Li+ affinities obtained for these two ligands are in good agreement (within 6 kJ mol−1) with recent values determined by the threshold collision‐induced dissociation method, and consistent with the Li+ basicity values first reported by Taft and co‐workers in 1990. Our study confirms that the previously suggested, and recently implemented, downward revision of Taft's original basicity scale by 10.9 kJ mol−1 is justified for ligands with revised basicities less than 151 kJ mol−1. However, for selected ligands with Li+ basicities greater than 151 kJ mol−1, including some of the six amides studied in this work, the reported discrepancy between theoretical and experimental estimates in the revised Li+ basicity scale of Burk et al. is likely to arise from experimental uncertainties. Copyright © 2002 John Wiley & Sons, Ltd.

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