Wade's rules are a well-established tool for the description of the geometry of inorganic clusters. Among others, they state that a decrease or increase in charge is always accompanied by a change in the number of skeletal electron pairs (SEPs). This work reports the synthesis of the first cationic chalcogenaboranes closo-[12-X-2-IPr-1-EB11H10]BF4 (X = H, I; E = S, Se 3a/b, 4a/b) featuring the same SEP count as their neutral precursors, EB11H11, but bearing a positive charge. This ionisation significantly enhances the activity towards the electrophiles. It unlocks reactivity with very weak bases and offers the control of the regioselectivity towards hard/soft bases by the modulation of LUMO. The localisation of the positive charge within the borane cluster has been confirmed experimentally, spectroscopically and theoretically.
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