Nucleophile Effects on the E2/S2 Competition for the X + CHCHCl Reactions: A Theoretical Study.

The effect of nucleophiles on the gas-phase E2/S2 competition is still not completely elucidated, despite its importance in chemistry. In the current work, the electronic structure calculations of prototypical reactions X + CHCHCl (X = OH, F, Cl, Br, and I) are performed at the MP2 level with aug-cc-pVDZ or ECP/d. The effects of nucleophiles on the competing E2 and S2 reactions in terms of the correlation between the barrier height and reaction energy, electronegativity of X, bond length, charge distribution, and proton affinity of anionic nucleophile X are explored and emphasized. As the nucleophile changes from OH to I, both S2 and E2 reactions become more exothermic, with the reaction energy in the ranges from -51.9 to 10.8 kcal mol (S2) and -36.8 to 38.0 kcal mol(E2). For X = F and OH, the sequence of reactivity for the four pathways is ret-S2 < syn-E2 < anti-E2 ∼ inv-S2. However, for X = Cl, Br, and I, the anti-E2 barrier is much higher in energy (17.1-29.4 kcal mol) than that of inv-S2. Energy decomposition analysis illustrates that the anti-E2 pathway possesses the highly destabilizing characteristic distortion, resulting in a larger reaction barrier and hence becoming a more unfavorable pathway than inv-S2. More interestingly, only ion-dipole complex exists in the entrance channel for reactions involving OH, Cl, Br, and I, and in contrast, a significant hydrogen-bonded complex formation is also revealed for X = F, which can further affect E2/S2 competition and atomic-level mechanisms, especially, for the isoelectronic nucleophile F and OH. It has been revealed here that electronegativity of central atoms in X and ionic radii of nucleophiles are the important factors affecting the entrance channel complex.