Xenon difluoride (XeF2) reacts with methanol to form an unstable reactive species CHgOXeF (1). Formaldehyde is produced quantitatively by disproportionation in the absence of unsaturated hydrocarbons or with unreactive alkenes. Hydrogen fluoride generated in situ complexes with 1 to form 2 which reacts with unsaturated hydrocarbons of intermediajte reactivity such as cisor trtms-l-phenylpropene (5c, 5t), indene (6), 2,3-dimethyl-l,3-butadiene (7), and norbornene (8) as an apparent fluorine electrophile and Markovnikov fluoromethoxy products are found.Reaction of XeF2 with methanol in the presence of boron trifluoride as catalyst forms the complex 3 which disproportionates to formaldehyde. Intermediate 3 reacts with unsaturated hydrocarbons of intermediate reactivity (5c, 5t, 6, 7, and 8) as a positive oxygen electrophile to give anti-Markovnikov fluoromethoxy products. However, very reactive (electron rich) alkenes such as dihydropyran ( 9) react rapidly with XeF2 to give a carbocation species before the intermediate 1 (or its complex 2 or 3) can be formed.Recently1® we reported on the methanolysis of xenon

Das aus Xenondifluorid und Methanol zugängliche, instabile Methoxyxenonfluorid (I) reagiert mit Olefinen zu Gemischen aus 1,2‐Difluoriden und 1‐Fluor‐2‐methoxyalkanen.