John M. Garver

TL;DR: These results show enhanced nucleophilicity for HOO(-) relative to "normal" alkoxides in three separate reaction series (methyl fluoride, anisole, and 4-fluoroanisole), validating an intrinsic origin of the α-effect.

TL;DR: The Solvation Rule fails the ultimate test of predicting gas phase results, where significantly smaller (more inverse) KIEs indicate the existence of a tighter transition state.

TL;DR: The application of complementary experimental methods, along with quantum chemical calculations, to a series of nitrogen-substituted azines sheds light on the influence of nitrogen atom substitution on the strength of C-H bonds in six-membered rings.

TL;DR: The gas phase reactivity of 1,3,5-triazine with several oxyanions and carbanions, as well as amide, was evaluated and data indicate a competitive nucleophilic aromatic addition pathway (SNAr) over a wide range of relative gas phase acidities to form strong anionic σ-adducts (Meisenheimer complexes).

TL;DR: In this article, the authors investigated the S N 2 reactions for methyl chloride of low exothermicity where the smaller thermodynamic component of the activation barrier may expose α-nucleophilicity.