The MeO-substituted derivative 5ad has not been formed. Except for the decomposed acetamide 5ae, all meta-and para-substituted derivatives 5af-5ak, among them derivatives with strong electron-withdrawing functionalities, could be synthesized in 39-69% yield. The electron-rich salt 5al was obtained in 75% yield using reaction conditions B. The harsher conditions were probably required due to a sterically hindered rotation of the benzimidazole moiety in the plane of the iodophenyl, which could also be observed in two rotamers of the iodoarene 4al (see ESI). C2-substituted benzimidazoles gave the moisture-sensitive, brominated salt 5am in an excellent yield of 89% and the carbon-substituted benzimidazoles 5an-5ap in 50-55%. The pyrazolesubstituted salt 5aq was obtained with 65% yield. Using an electron-rich 4,5dimethylbenzimidazole yielded 5ar in 85%. Even under harsher reaction conditions, the corresponding electron-deficient dibrominated salt 5as could not be obtained. This further demonstrates the crucial influence of the electronic properties on the reactivity of those substrates. Electron deficiency is particularly counterproductive for the final cyclization step. To prove the influence of the electron-rich dimethylated benzimidazole, this moiety combined with the chlorinated and brominated iodoarene gave the corresponding salts 5at-5au in good yields under milder reaction conditions, in particular in direct comparison to the unsubstituted analogs 5ar-5as. N-substituted iodoarenes were then used to create dicationic iodonium salts. The N-Me and N-Ph iodonium-benzimidazolium salts 5av-5aw were obtained in 47% and 88% yield. Installation of additional ortho-methyl groups resulted in formation the sigma-hole-protected N-substituted salts 5ax-5az in up to 97% yield. Next, the iodonium center was stabilized through an additional N-coordination via ortho-pyrazole substitution, giving the iodonium salts 5ba-5bb in 88% and 50% yield. The oxidation of indazoles 5bc-5bd was not as efficient, with yields of 24% and 44%. In the latter case, the initially generated hydroxy-iodonium salt is stabilized via the indazole nitrogen. The steric hindrance of the methyl group is likely destabilizing this intermediate by an out-of-plane distortion and hence accelerating the cyclization.