Abstract
A new method for production of chloride ion adducts, MCl, via a sequence of bimolecular ion molecule reactions involving chloroformate esters is described. These reactions have been used in trapped-ion ion cyclotron resonance thermal equilibrium studies to determine the relative chloride ion affinities of twenty compounds with Cl binding energies in the range 10–25 kcal mol−1. The present results are found to be in good agreement with chloride affinities obtained by other methods. The resulting chloride affinity scale establishes a convenient framework for the systematic investigation of effects of molecular structure and chemical properties on the binding energy of Cl to both Lewis and Brønsted acids.

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