2,4,6-Trimethylpyridine–bishydrofluoride: a novel fluorinating reagent for organo transition-metal alkyls

Abstract

Complexes [M(η⁵-C₅Me₅)F₃](M = Zr 2, Hf 5), [Zr(η⁵-C₅H₅)F₂] 7 and [Hf(η⁵-C₅Me₅)F₂] 8 are obtained by treating the corresponding metal alkyls with [tmpy-(HF)₂](tmpy = 2,4,6-trimethylpyridine); using an excess of [tmpy-(HF)₂] in the preparation of 2 and 5 leads to the complexes [Htmpy][{M(η⁵-C₅Me₅)F₂}(µ-F)₃](M = Zr 3, Hf 6), respectively and a crystal structure determination of 3 confirms its ionic nature; [Ti(η⁵-C₅Me₅)Cl₂F] 10 and 2 were synthesised also from their corresponding alkyls by alkyl–fluorine exchange using Me₃SnF.