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033(00)22 reacts with ethylene oxide in the presence of Br" to give two of the few known dioxycarbene cluster compounds, 0s3(C0)jj(=COCH^CH^). I , and 053(00)io(=cOCH^CH^)2, II . The structure of II , established by X-ray diffraction studies, shows the dioxycarbene ligands to be in terminal, equatorial positions. Investigations of reactions of the dioxycarbene ligand showed that Fe(00)4(=OOOH2CH20), III, decomposes with evolution of OO2 and ethylene, but reacts with oxidizing agents, Me3N0 or O2, to produce ethylene carbonate. The reaction of III with H2 gas gives 1,3-dioxolane. In exploratory studies, ethylene oxide, 00 and H2 In the presence of Pt, Pd and Rh catalysts were found to give 1,4dioxane, 2-niethyl-1,3-dioxolane and 2-ethyl-l,3-d1oxolane.

Transition metal carbene complexes and platinum-catalyzed substitution of metal carbonyls