Synthesis of Mono‐, Bis‐ and Tris(pentafluoroethyl)tin Derivatives, (C 2 F 5 ) 4− n SnX n (X=Ph, Me, Cl, Br, Cp; n =1–3)

For (pentafluoroethyl)phenylstannanes, (C 2 F 5 ) 4− n  SnPh n ( n =1–3), and dimethylbis(pentafluoroethyl)stannane, (C 2 F 5 ) 2 SnMe 2 , a high yield synthesis was developed by the use of LiC 2 F 5 as a C 2 F 5 transfer reagent. The treatment of these products with gaseous hydrogen chloride or hydrogen bromide afforded (C 2 F 5 ) 4− n SnX n (X=Cl, Br; n =1–3) in good yields. The (pentafluoroethyl)stannanes were fully characterized by 1 H, 13 C, 19 F and 119 Sn NMR, IR spectroscopy and mass spectrometry. The treatment of the (pentafluoroethyl)tin halides (C 2 F 5 ) 4− n SnX n with 1,10‐phenanthroline (phen) led to the formation of the corresponding octahedrally coordinated complexes [(C 2 F 5 ) 4− n SnX n (phen)], the structures of which were elucidated by X‐ray diffraction analyses. The bromostannane (C 2 F 5 ) 3 SnBr reacted with sodium cyclopentadienide to give the ( η 1 ‐cyclopentadienyl)tris(pentafluoroethyl)stannane, (C 2 F 5 ) 3 SnCp, for which single‐crystal X‐ray diffraction analysis could be performed. The coupling constants 1 J ( 119 Sn, 13 C) and 2 J ( 119 Sn, 19 F) of all new stannanes are strongly correlated and sensitive to the substitution pattern at the tin atom. For both coupling constants a negative sign could be assigned.