Synthesis, Structure, and Reactivity of a Terminal Organozinc Fluoride Compound: Hydrogen Bonding, Halogen Bonding, and Donor–Acceptor Interactions

[Tris(2-pyridylthio)methyl]zinc fluoride, [κ(4)-Tptm]ZnF, the first example of an organozinc compound that features a terminal fluoride ligand, may be obtained by the reactions of either [Tptm]ZnX (X = H, OSiMe3) with Me3SnF or [κ(4)-Tptm]ZnI with [Bu(n)4N]F. Not only is the fluoride ligand of [κ(4)-Tptm]ZnF susceptible to coordination by B(C6F5)3 to give the adduct [κ(4)-Tptm]ZnFB(C6F5)3, but it is also an effective hydrogen bond and halogen bond acceptor. For example, X-ray diffraction studies demonstrate that [κ(4)-Tptm]ZnF forms an adduct with water in which hydrogen bonding between the fluoride ligands and water molecules serves to link pairs of [κ(4)-Tptm]ZnF molecules with a [F···(H-O-H)2···F] motif. Furthermore, (1)H and (19)F NMR spectroscopic studies provide evidence for hydrogen bonding and halogen bonding interactions with indole and C6F5I, respectively.