Selecting the N-fluoropyridinium triflate 1 catalysed reaction between N-arylimine 2 and ethyl diazoacetate (EDA) 3 as our model reaction, we initiated a computational mechanistic study to determine if the reaction would work in the absence of N-fluorinated organocatalyst 1. These calculations show that without 1, the activation free energy barriers of both concerted (TSuncat: 45.7 kcal mol -1 ) and stepwise mechanisms are prohibitively high (see Figure in SI); this is consistent with the indispensable role 1 has in activating 2 towards reaction with EDA and aziridine formation . Next, we examined whether 1 could facilitate catalysis and aziridine synthesis via a 'classic' F-halogen bond. In line with results reported by Lectka, Dudding, and coworkers , preliminary analysis of the electrostatic potential map of 1 revealed a weak σ-hole along the extension of the N-F bond (see Figure in SI). This suggests that 1 has the potential to form an F-halogen bond with 2. However, further analysis of our calculations allowed us to conclude that the stability of the F-halogen bond complex CP1 formed from 1 and 2 would not be strong enough to compensate for entropy loss, which would result in the endergonic formation of CP1 with a ΔG of 9.1 kcal mol -1 . This means that the activation free energy barrier for the F-halogen bondcatalyzed aziridine synthesis via TSFHB (Figure ) is even higher than for the reaction without a catalyst (TSFHB: 53.8 kcal mol -1 vs. TSuncat: 45.7 kcal mol -1 ). In summary, these results established that 1, acting as a F-halogen bond catalyst, cannot effectively lower the free energy barrier for aziridine synthesis when starting materials 1 and 2 are employed.