The Diels - Alder cycloadditions of tetrazines (1) with alkynes (2) are expected to give bicyclic adducts (3). Kinetic measurements of the cycloadditions of 1a and 1b with 2a give ΔG ‡ = 19.2 ± 1.0 and 11.5 ± 1.2 kcal/mol, respectively. Stopped-flow UV studies on the reaction of 1b with 2a show an isosbestic point at 428 nm; this places an upper limit of 11.6 ± 2.6 kcal/mol on ΔG ‡ for loss of N 2 from the putative bicyclic intermediate 3b. Calculations (B3LYP/6-31G(d,p) + ZPVE) of transition structures for the reaction of tetrazinediacid 1d with propynylamine 2c are consistent with the experimental results for the reaction of 1b with 2a. This and several related model systems reveal two interesting features of the calculated energy surfaces. First, there may be no barrier for the loss of nitrogen from structures 3 and thus there may be two sequential transition states. This also extends Berson's correlation of activation energy with reaction energy in pericyclic reactions to significantly lower barriers. Second, for the cycloaddition of 4e and 2c, there is neither an intermediate nor a transition state between TS3e and the final product 6e. It appears that the energy surface "turns a corner" in the vicinity of a structure resembling 5e. This is not a mathematically well-defined point but has chemical consequences in that the overall exothermicity of the reaction from 4e to 6e is not felt in TS3e.