Mercury(II)
anions derived from the F5TeO- (teflate) group were synthesized and structurally characterized. The
salts, [N(CH2CH3)4]2[Hg(OTeF5)4], [N(CH3)4]3[Hg(OTeF5)5], [N(CH2CH3)4]3[Hg(OTeF5)5], [N(CH3)4]2[Hg2(OTeF5)6], Cs2[Hg(OTeF5)4]·Hg(OTeF5)2, and {Cs3[Hg2(OTeF5)7]·Hg(OTeF5)2}·4SO2ClF, were obtained by reaction of Hg(OTeF5)2 with [M][OTeF5] (M = [N(CH3)4](+), [N(CH2CH3)4](+), Cs(+)) and were characterized by low-temperature single-crystal X-ray diffraction and low-temperature Raman spectroscopy. Unlike in the extensively
fluorine-bridged solid-state structures of [HgF3](-) and [
HgF4](2-), the less basic and more sterically demanding teflate
ligands of the Hg(II)
anions show less tendency to bridge. The
anions exhibit a variety of structural motifs, ranging from well-isolated tetrahedral [Hg(OTeF5)4](2-) and square-pyramidal [Hg(OTeF5)5](3-) to the chain structures, [Hg2(OTeF5)6](2-) and [Hg2(OTeF5)7](3-)·Hg(OTeF5)2. The geometrical parameters and vibrational frequencies of [Hg(OTeF5)4](2-) (S4), [Hg(OTeF5)5](3-) (C1), and [Hg2(OTeF5)6](2-) (D2)
anions, as well as the hypothetical [Hg3(OTeF5)8](2-) (C1)
anion, were calculated using density functional theory methods (PBE1PBE/def2-TZVPP), which aided in the assignment of the Raman spectra of [Hg(OTeF5)4](2-), [Hg(OTeF5)5](3-), [Hg2(OTeF5)6](2-), and Cs2[Hg(OTeF5)4]·Hg(OTeF5)2. The calculated geometries were used to assess the effects of solid-state interionic interactions on the
anion geometries. For the most part, the gross gas-phase trigonal bipyramidal (
tbp) geometry of [Hg(OTeF5)5](3-) adheres to the predicted VSEPR geometry but contrasts with the solid-state
anion structures, which have square-pyramidal geometries or geometries that lie between square pyramidal- and
tbp-geometries. However, the bond length order calculated for the Hg-O bonds of
tbp-[Hg(OTeF5)5](3-), Hg-Oeq > Hg-Oax, is opposite to that predicted by the VSEPR model of molecular geometry. Natural bond orbital analyses provided the associated Mayer bond orders, Mayer valencies, and natural population analysis charges.