The solvent dependency of the F-19 NMR shifts of the fluoride anion in CH3OH, H2O, CH3OCH3, CHCl3, CH2Cl2, CHF3, CH3CN, CH3NO2, (CH3)(2)SO, and CH3COCH3 solutions was studied at the MP2/6-31 ++G(d, p) and B3LYP/6-31 ++G(d, p) levels of theory and compared to the experimental values. It is shown that the free gaseous fluoride anion is most shielded. The stepwise build-up of a solvation sphere was modeled for the F-/nH(2)O system and results in a progressive deshielding of the F- nucleus with an increasing number of water ligands. The first solvation sphere of F- is comprised of six or seven monodentate water molecules. The F-...H bond distances increase from 1.42 Angstrom in the monohydrate to 1.69-1.87 and 1.82 Angstrom in the penta- and hexahydrates, respectively, and the transfer of negative charge from F- to the water ligands reaches its maximum for the tetrahydrate. The wide range of about 70 ppm observed for the chemical shift of F- in different solvents and the order of deshielding are confirmed by model calculations. Furthermore, it is shown that the deshielding observed for different solvents does not correlate with the calculated binding energies between F- and the corresponding solvent molecules, but parallels the increase in the calculated shielding anisotropy in the case of monodentate solvent F- adducts. Since the calculated shielding anisotropy can be taken as a qualitative measure for the paramagnetic shielding, the large solvent dependency of the F- shifts is best explained by the varying amounts of solvent induced paramagnetic shielding. The preferred structure of the F-.CH3OH adduct involves hydrogen bridging through the hydroxyl and not the methyl group, and the minimum energy structures of F-.CH3SOCH3 and F-.CH3COCH3 exhibit bidentate solvent coordination. In solid fluorides, the chemical shift of F- spans more than 190 ppm and an increasing cation size results in increased deshielding. As previously shown, this deshielding is due to the electronic overlap effects. The MAS F-19 NMR spectra of solid N(CH3)(4)F and P(CH3)(4)F were also measured. The F- anion in the P(CH3)(4)(+) salt is 19 ppm less shielded than in the N(CH3)(4)(+) salt in accord with the increased cation size. However, in spite of its large size the deshielding caused by the N(CH3)4+ cation is only comparable to that of Rb+ due to the methyl groups not providing as good an overlap as the smaller but softer Cs+ cation. These results show that in both, the solid state and in solution, the chemical shift of F- is not a measure of its nakedness and that the fluoride anion is far from being naked. (C) 2002 Elsevier Science B.V. All rights reserved.
