Bew and coworkers revealed an intriguing method in 2009 for racemic, predominantly cis-aziridine synthesis. Using N-fluoropyridinium triflate 1 as the catalyst (10 mol%) its ability to activate structure and function diverse N-aryl imines enabled azirdine formation with the weak nucleophile ethyl diazoacetate (Figure ) . Experiments conducted under vigorous water exclusion and analysis via mass spectroscopy ruled out the possibility of exclusive or competing Brønsted acid catalysis from 'contaminating' pyridinium triflate, generated in situ from trace amounts of water. Since the 2009 publication, the use of 1 has generally been considered to be the first report of a reaction catalysed via F-halogen bonding interactions associated with the highly electrophilic F-cation , even though this mechanism was not originally proposed. Moreover, and pertinent to the work reported here, a detailed mechanism of the aziridination reaction involving 1 and its role in halogen bonding catalysis generating 4 remains unclear. To gain a better understanding of how 1 behaves in fluorinecentered halogen bonding, we conducted an in-depth computational study to delineate the mechanism of this intriguing reaction. Our comprehensive computational analysis reveals, rather unexpectedly, that initiation of the aziridination proceeds via efficient transfer of an F-cation rather than a presumed F-halogen bond interaction. This surprising and unusual finding led us to further extend our analysis to alternative archetypal halogen-bondingcatalysed transformations (Figure ). Remarkably, these studies suggest that halogen cation transfer could, potentially, serve as a new generic and alternative pathway for effective and mild reaction activation. Our findings call into question long-held beliefs about the role Nfluoropyridinium salt 1 has in reaction activation processes originally thought to involve the creation and exploitation of halogen bonds. The discovery of F-cation transfer as a unique activation mode means chemists now have an additional tool in their synthesis 'toolbox' for the creation of innovative catalysts that efficiently mediate new reactions, yielding novel molecular architectures.