S(N)2 versus E2 Competition of F(–) and PH(2)(–) Revisited

[Image: see text] We have quantum chemically analyzed the competition between the bimolecular nucleophilic substitution (S(N)2) and base-induced elimination (E2) pathways for F(–) + CH(3)CH(2)Cl and PH(2)(–) + CH(3)CH(2)Cl using the activation strain model and Kohn–Sham molecular orbital theory at ZORA-OLYP/QZ4P. Herein, we correct an earlier study that intuitively attributed the mechanistic preferences of F(–) and PH(2)(–), i.e., E2 and S(N)2, respectively, to a supposedly unfavorable shift in the polarity of the abstracted β-proton along the PH(2)(–)-induced E2 pathway while claiming that ″...no correlation between the thermodynamic basicity and E2 rate should be expected.″ Our analyses, however, unequivocally show that it is simply the 6 kcal mol(–1) higher proton affinity of F(–) that enables this base to engage in a more stabilizing orbital interaction with CH(3)CH(2)Cl and hence to preferentially react via the E2 pathway, despite the higher characteristic distortivity (more destabilizing activation strain) associated with this pathway. On the other hand, the less basic PH(2)(–) has a weaker stabilizing interaction with CH(3)CH(2)Cl and is, therefore, unable to overcome the characteristic distortivity of the E2 pathway. Therefore, the mechanistic preference of PH(2)(–) is steered to the S(N)2 reaction channel (less-destabilizing activation strain).