Mehrfachbindungen zwischen Hauptgruppenelementen und übergangsmetallen, CVIII. Stöchiometrische und katalytische Oxidation elektronenarmer Olefine mit Osmiumtetraoxid: Eine neue Oxidationsmethode für Fluorolefine

Multiple Bonds between Atoms of Main Group Elements and Transition Metals, CVIII. — Stoichiometric and Catalytic Oxidation of Electron‐poor Olefins with Osmium Tetraoxide: A Novel Oxidation Method for Fluoroolefins In contrast to current opinion, osmium tetraoxide reacts even with very electron‐poor olefins. For example, both partially and fully fluorinated osmate(VI) esters 2 are thus formed from fluoroolefins 1 by cycloaddition. Hydrolysis of the osmate(VI) esters leads to the corresponding 1,2‐diols 3 and, eventually, consecutive fluoroorganic products by HF elimination. A catalytic version of this route opens a new, general, and efficient entry to oxidation products in fluoroolefin chemistry. Tetrahalide ethylene derivatives of formula py 2 O 2 Os(OCX 2 CX 2 O) (X = Cl, F) split off oxalyl halide upon thermal treatment with the complexes py 2 O 2 OsX 2 thus being formed in good yields.