with MeOTf resulted in a selective benzimidazole N-methylation. A reaction on the pyrazole nitrogen is impeded due to its coordination with the iodanes σ-hole (Scheme 2a). Besides nitrogen-substitution, the benzimidazole C-2 of the dicationic salts is a reactive position for oxidative transformations. The reaction of the iodine-protected benzimidazolium salts 5ax-5az and 12 under different oxygen sources revealed K2CO3 and NCS as the best system to form the benzimidazole-2-ones 13a-13d in 18-48%, with the best yield using the stabilized salt 12 (Scheme 2b). Here, This reactivity demonstrates the highly stabilizing effect of N-heterocycles on hypervalent iodine species. Furthermore, the formed 2-amino benzimidazoles reveal new access to potential bioactive compounds. Even the formation of the free guanidine 16 via deprotection of the Boc-group was possible in quantitative yields.