The results of the 2-chloroacetamides show no correlation for both the warhead-associated electrophilicity index and MAAs. This behavior is extensively studied in the work of Hermann et al. , and their arguments reflect the change from the Michael-type nucleophilic additions to an S N 2 reaction. Specifically, they show that the LUMO energy correlates with the bond strength of both the C-Cl and C-SMe bonds. Thus, the electrophilicity index fails to capture the energetics of the reaction due to the simultaneous bond formation and rupture. However, the calculated MAAs behave similarly despite not depending on FMO energies, which raises questions about their reasonings. Furthermore, when using CH 3 S - instead of CH - 3 , we again find no correlation with an R 2 coefficient of 0.01 as seen in the supporting information. This result is surprising as it contradicts the Bell-Evans-Polanyi principle (i.e., the change in activation energy for similar reactions being proportional to the change in reaction enthalpy), indicating that further analysis of the transition state structures should be carried out.