Abstract
AbstractTransition‐metal hexafluorides do not exhibit fluoride‐ion donor properties in the absence of donor ligands. We report the first synthesis of donor‐stabilized [MF5]+ derived from a transition‐metal hexafluoride via fluoride‐ion abstraction using WF6(L) (L=2,2′‐bipy, 1,10‐phen) and SbF5(OSO) in SO2. The [WF5(L)][Sb2F11] salts and [WF5(1,10‐phen)][SbF6]⋅SO2 have been characterized by X‐ray crystallography, Raman spectroscopy, and multinuclear NMR spectroscopy. The reaction of WF6(2,2′‐bipy) with an equimolar amount of SbF5(OSO) reveals an equilibrium between [WF5(2,2′‐bipy)]+ and the [WF4(2,2′‐bipy)2]2+ dication, as determined by 19F NMR spectroscopy. The geometries of the cations in the solid state are reproduced by gas‐phase geometry optimizations (DFT‐B3LYP), and NBO analyses reveal that the positive charges of the cations are stabilized primarily by compensatory σ‐electron donation from the N‐donor ligands.
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