Abstract
The standard Gibbs energy changes for the halide transfer processes in the gas phase have been determined by means of Fourier transform ion cyclotron resonance mass spectrometry (FT ICR): 1- Ad- X(g)+ R +( g)→1- Ad +( g)+ R- X(g) X = Halogen; l-Ad = 1-Adamantyl; R-X = CCl 4 (1), CBr 4 (2), CI 4 (3) and CBr 3F (4). To this end, systematic use was made of the dissociative proton attachment method (DPA) [J-L.M. Abboud et al., J. Am. Chem. Soc. 116 (1994) 2486–2492.], which allowed one to experimentally determine the onsets for reactions: R-X(g)+ BH +( g)→ R +( g)+ HX(g)+ B(g) R = CCl 3, CBr 3, CI 3, CBr 2F, 1-Ad. In the case of 4, two different onsets were determined, respectively, corresponding to the formation of CBr 2F +(g) and CBr 3 + (g). The thermodynamics of several reactions (see the first equation above) were studied at the MP2/6–31G(d) level. The results agree very satisfactorily with the experimental results.
Published Version
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