The two triflate anions in the outer sphere point directly at the central carbon C1 [mean S1-O1-C1 and S1'-O1'-C1 angle: 163.2(1)º], albeit from a considerable distance away [mean of C1-O1 and C1-O1': 3.020(3) Å] (Fig. ). This suggests that their approach to the central carbon is effectively impeded by the large steric profile of the flanking NHI substituents (for space-filling model see Table ). Secondary interactions between the triflate anions and the CAAC carbon atoms also exist, but at an even further distance [mean of C2-O2 and C2'-O2': 3.995(3) Å]. These observations clearly indicate that the central C1 is the dominant electrophilic site, while the CAAC carbon atoms (C2 and C2') play a secondary role. DFT calculations performed at the r 2 SCAN-3c level of theory accurately reproduced the structural parameters of 1 2+ . Natural population analysis (NPA) reveals a large positive charge on the central C1 (+0.73), confirming that it is indeed the predominant electrophilic site of the molecule (Fig. ). On the other hand, the peripheral C2 and C2' (+0.56) share some of the positive charge through allylic-type delocalization. Wiberg bond indices (WBI) suggest double bond characters, albeit to a larger degree for the central C1-N1 and C1-N1' (mean: 1.92) than the terminal C2-N1 and C2'-N1' (mean: 1.29), consistent with an overall cumulene-type system with contiguous double bonds across the CNCNC unit (Fig. ). As for the molecular orbital picture, the LUMO and LUMO+1 could be viewed as the orthogonal vacant p(p)-type orbitals on central C1, with contributions from C2 and C2' (Fig. ). Importantly, these orbitals possess Möbius-type helicity, as with the frontier orbitals of [4]cumulenes , confirming the cumulenic nature of 1 2+ . Interestingly, the LUMO+2 bears a strong resemblance to the HOMO (lone pair orbital) of bis(imino)carbene 1 7 , consistent with the notion that 1 2+ is the doubly oxidized analogue of carbene 1.