Recently, it was shown that samarocene oxide [Cp*2SmO-SmCp*(2)] with Cp* = C5Me5 could react with organic and inorganic anhydrides. The reactions of [Cp*Sm-2-O-SmCp*(2)] with SO2 and SO3 are reported using DFT calculations and compared with the reactivity of CO2. These reactions exhibit similar features yielding [Cp*(2)-Sm-(mu-eta(1):eta(2)-OSO2)-SmCp*2] similar to [Cp*(2)-Sm(mu-eta(1):eta(2)-OCO2)-SmCp*(2)] and [Cp*(2)-Sm-(mu-eta(2):eta(2)-O2SO2)-SmCp*(2)] complexes.