Multiple protonation of a stable species is investigated as an effective way of forming light, highly charged systems. As a test of these ideas, we report the structures, frequencies and thermochemistry of the metastable species B2H33+ at the G2 level of theory with additional calculations at the QCISD(T)/6-311G(d,p) level. The lowest energy isomer is a linear, singly bridged species while the second lowest isomer is triply bridged. In examining the thermochemistry related to the fragmentation of B2H33+, we report results for most of the mono-, di- and triprotonated forms of B, B-2 and B-2(+). Suprisingly, Science B.V. All rights reserved.