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General Procedure. The reactions were carried out in an all-Pyrex-glass reactor, with stopcocks and joints lubricated with "Halocarbon" grease. A stream of dry nitrogen (2 1/hr) saturated with fluorine fluorosulfate at -78°(~50 mm) was bubbled into the haloalkane (or haloalkene) cooled also at -78°.When all the fluorine fluorosulfate had reacted and the inert gas was pumped out of the reactor at -190°, the liquid was warmed up to room temperature. Then it was treated with a saturated solution of sodium bicarbonate and repeatedly washed with distilled water. Finally it was dried over anhydrous potassium carbonate. The components of the liquid mixture were determined by vpc chromatography in an F & M model 810 instrument equipped with a thermal conductivity detector and an analytical column (1.65 mm X 1.8 m) packed with Chromosorb W (AW-TMCS) impregnated with 10% Carbowax 20 M.The reaction products could be separated with a preparative column (12.5 mm X 2.40 m) packed with Chromosorb W (AW-TMCS) impregnated with 10% silicone gum rubber SE-30.The infrared spectra of the products were obtained on a Perkin-Elmer Model 337 spectrophotometer using cells equipped with KBr windows. Nuclear magnetic resonance spectra were recorded on a DP-60 Varían Associates instrument. Trichlorofluoromethane and tetramethylsilane were used as internal standards. The vapor pressures of the products were measured with a mercury manometer, using a quartz spiral as a null instrument.Molecular weights were determined by the gas chromatographic method.8 9 Elemental analyses were carried out making use of microchemical techniques.10 Preparation of Dichloromethyl Fluorosulfate (I). The reaction of 0.06 mol of fluorine fluorosulfate and 0.5 mol of chloroform yielded 80% product I and 13% trichlorofluoromethane.The reaction is rapid and exothermic. Compound I is a colorless liquid which slowly decomposes at room temperature; mp -66.0 ± 0.5°. The vapor pressure is given by log p(mm) = 8.00-1890/7X°K) (between 2 and 20°) and A/fvap = 8.6 kcal mol"1. The Trouton constant is 23.4 eu; bp (extrapolated) 95.8°. Anal. Caled for CH03-

Der Komplex (Ia) wird in einer Ausbeute von ca. 32% durch Reaktion von (NH4),OsC16 mit Zn‐Staub und NH3 unter Ar und Zugabe von KJ erhalten.