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S2O2, the unstable initial product of SO decomposition in the gas phase, has been trapped for the first time by complexation. With the isolation of the surprisingly stable thiirane S-oxide complex 1, it was further demonstrated that C2H4SO first decomposes after coordination to a metal. Ethylene is eliminated from 1 in toluene only at 110°C, whereupon the S2O2 complex 2 is formed.