TRIMETHYLTIN FLUORIDE - A NEW FLUORINATING REAGENT FOR THE PREPARATION OF ORGANOMETALLIC FLUORIDES

Me3SnF (1) reacts with Cp'MCl3 to give Cp'MF3 (2, Cp' = C5Me5, M = Ti; 2a, Cp' = C5Me4Et, M = Ti; 2b, Cp' = C5H5, M = Ti; 2c, Cp' = C5H4Me5, M = Ti; 3, Cp' = C5Me5, M = Zr; 4, Cp' = C5Me5, M = Hf) in high yields. The reaction of Cp2TiCl2, [C5H3(Me)(SiMe3)]2ZrCl2, and (C5Me5)2HfCl2 with Me3SnF yields Cp2TiF2 (5), [C5H3(Me) (SiMe3)]2ZrF2 (6), and (CsMe5)2HfF2 (7), respectively. Treatment of (Cp*TiClO)3 (Cp* = C5Me5) with Me3SnF leads to the eight-membered ring (Cp*TiFO)4 (8). The reaction of the organotitanium(III) chlorides (Cp2TiCl)2 (Cp = C5H5), [(C5H4Me)2TiCl]2, and Cp*2TiCl with Me3SnF gives the corresponding fluorides (Cp2TiF)2 (9), [(C5H4Me)2TiF]2 (10), and Cp2*TiF (11), respectively. An alternative method for the preparation of compounds 9 and 10 is the reduction of Cp2TiF2 and (C5H4Me)2TiF2, respectively, using sodium amalgam. The structures of 2c, 3, 4, and 10 were determined by single-crystal X-ray diffraction. Compounds 3 and 4 are isostructural and form tetramers in the solid as well as in solution. 10 is a fluorine-bridged dimer in the crystalline state.