Abstract Selenides of the type R 1 Se–EMe 3 (E= Si, Ge, Sn, Pb) react with xenon difluoride by cleavage of the Se–E bond to yield the R 1 Se–F intermediate and the fluorides Me 3 E– F, whereas the Se–C bond in PhSe–tBu (E= C) is stable against XeF 2. The presence of R 1 Se–F intermediates is confirmed by addition to acetylenes (4-octyne, 3-hexyne). Thus, the fluoroselenenylation of acetylenes gives fluoro (organylseleno) olefins in preparative ...