Trimethyltin fluoride: A new fluorinating reagent for the preparation of organometallic fluorides

Article abstract of DOI:10.1021/om00016a030

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′ = C₅H₄Me, 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 (C₅Me₅)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.