Ring-stacked boranes of the B10H102- and B12H122- type, when substituted with lone pair bearing groups such as -O, -NH, and -S at the para positions, are theoretically shown to exhibit exopolyhedral multiple bonding on oxidation. Successive removal of two and four electrons from the parent BnHn-2X2 results in highly varied and intriguing skeletal deformations that are explained using fragment molecular theory.