화학공학소재연구정보센터
Inorganic Chemistry, Vol.56, No.20, 12581-12593, 2017
Syntheses and Characterization of W(NC6F5)F-5(-) and W-2(NC6F5)(2)F-9(-) Salts and Computational Studies of the W(NR)F-5(-) (R = H, F, CH3, CF3, C6H5, C6F5) and W-2(NC6F5)(2)F-9(-) Anions
Convenient preparative routes to fluorido-[(pentafluorophenyl)imido]tungstate(VI) salts have been developed. The reaction of WP6 center dot NC5H5 or [N(CH3)(4)][WF7] with C6F5NH2 results in quantitative formation of the C5H5NH+ or N(CH3)(4)(+) salt of the W(NC6F5)F-5(-) anion, respectively. The dissolution of [C5H5NH] [W(NC6F5)F-5] in anhydrous HF results in the formation of [C5H5NH] [W-2(NC6F5)(2)F-9]. These salts have been comprehensively characterized in the solid state by X-ray crystallography and Raman spectroscopy and in solution by F-19 and H-1 NMR spectroscopy. The crystal structures of the W(NC6F5)F-5(-) salts reveal conformational differences in the anions, and the F-19 NMR spectra of these salts in CH3CN reveal coupling of the axial fluorido ligand to the N-14 nucleus of the imido ligand. In addition, density functional theory (DFT-B3LYP) calculations have been performed on a series of W(NR)F-5(-) anions (R = H, F, CH3, CF3, C6H5, C6F5) and the W-2(NC6F5)(2)F-9(-) anion, including gas-phase geometry optimizations, vibrational frequencies, molecular orbitals, and natural bond orbital (NBO) analyses.