Effects of Methyl Substitution and Leaving Group on E2/S(N)2 Competition for Reactions of F(−) with RY (R = CH(3), C(2)H(5), (i)C(3)H(7), (t)C(4)H(9); Y = Cl, I)

The competition between base-induced elimination (E2) and bimolecular nucleophilic substitution (S(N)2) is of significant importance in organic chemistry and is influenced by many factors. The electronic structure calculations for the gas-phase reactions of F(−) + RY (R = CH(3), C(2)H(5), (i)C(3)H(7), (t)C(4)H(9), and Y = Cl, I) are executed at the MP2 level with aug-cc-pVDZ or ECP/d basis set to investigate the α-methyl substitution effect. The variation in barrier height, reaction enthalpy, and competition of S(N)2/E2 as a function of methyl-substitution and leaving group ability has been emphasized. And the nature of these rules has been explored. As the degree of methyl substitution on α-carbon increases, the E2 channel becomes more competitive and dominant with R varying from C(2)H(5), (i)C(3)H(7), to (t)C(4)H(9). Energy decomposition analysis offers new insights into the competition between E2 and S(N)2 processes, which suggests that the drop in interaction energy with an increasing degree of substitution cannot compensate for the rapid growth of preparation energy, leading to a rapid increase in the S(N)2 energy barrier. By altering the leaving group from Cl to I, the barriers of both S(N)2 and E2 monotonically decrease, and, with the increased number of substituents, they reduce more dramatically, which is attributed to the looser transition state structures with the stronger leaving group ability. Interestingly, ∆E(0)(‡) exhibits a positive linear correlation with reaction enthalpy (∆H) and halogen electronegativity. With the added number of substituents, the differences in ∆E(0)(‡) and ∆H between Y = Cl and I likewise exhibit good linearity.