The circumambulatory rearrangements of some 8,8-dimethylhomotropylium cations and their corresponding iron tricarbonyl complexes have been examined. 8,8-Dimethylhomotropylium cation, 4, has been prepared by protonation of 8,8-dimethyl-bicyclo[5.1.0]octa-3,5-dien-2-ol in FSO3H/SO2ClF. Evidence for homoaromatic delocalization in 4 was found in its characteristic 1H nmr spectrum, particularly when this was compared to that of the non-cyclically delocalized 8,8-dimethyl-bicyclo[5.1.0]octadienyliron tricarbonyl complex 7. Cation 4 was found to be stable at low temperatures but to isomerize to isopropyltropylium ion, 8, at −50 °C, [Formula: see text] The specifically deuterated cation 4D was prepared and a slow circumambulation of C8 around the basal 7-membered ring of this cation was found to occur at −90 °C. The free energy of activation for this circumambulation is 14.5 kcal/mol. Homotropylium cation 4 was also prepared by protonation of 8,8-dimethylbicyclo[3.2.1]octa-3,6-dien-2-ol, 14, at −120 °C. No evidence for the presence of the corresponding bicyclo[3.2.1]octadienyl ion 12 was obtained. The 2,8,8-trimethylhomotropylium cation, 17, was prepared and shown to undergo a circumambulatory rearrangement to give the 4,8,8-trimethyl substituted cation 20 as the major product. In this trimethyl series it also proved possible to generate the 2,8,8-trimethylbicyclo[3.2.1]octadienyl cation, 18, and observe its 1H nmr spectrum at very low temperatures (−116 °C). The proton chemical shifts of 18 suggest that the charge is predominantly located on the 3-carbon bridge. Cation 18 isomerized to 17, 20, and other products at temperatures above −100 °C. The 2,8,8-trimethylbicyclo[5.1.0]octadienyliron tricarbonyl complex 22 was also shown to undergo a circumambulatory rearrangement in which both C8 and the Fe(CO)3 grouping migrate.