R(f)SeH 1 is obtained in a single pot reaction of R(f)Li [R(f) = 2,4,6-tris(trifluoromethyl)phenyl] with elemental seleniun and following treatment with HBF4. 1 gave the first crystal structure of a selenane. Reaction of 1 with M[N(SiMe3)2]2 (M = Zn, Pb) in the molar ratio of 2:1 yielded the metal selenophenolates Zn(SeR(f))2 . HN(SiMe3)2 2 and [Pb(SeRf)2]2 3. 2 crystallizes as hexamethyldisilazane adduct, 3 as a dimer.