The fluoride ion donor properties of TcO2F3 and ReO2F3 toward AsF5, SbF5, and XeO2F2 have been investigated, leading to the formation of TcO2F3. PnF(5) and ReO2F3. PnF(5) (Pn = As, Sb) and TcO2F3. XeO2F2, which were characterized in the solid state by Raman spectroscopy and X-ray crystallography. TcO2F3. SbF5 crystallizes in the monoclinic system P2(1)/n, with a = 7.366(2) Angstrom, b = 10.441(2) Angstrom, c = 9.398(2) Angstrom, beta = 93.32(3)degrees, V = 721.6(3) Angstrom(3), and Z = 4 at 24 degrees C, R-1 = 0.0649, and wR(2) = 0.1112. ReO2F3. SbF5 crystallizes in the monoclinic system P2(1)/c, with a = 5.479(1) Angstrom, b = 10.040(2) Angstrom, c = 12.426(2) Angstrom, beta = 99.01(3)degrees, V = 675.1(2) Angstrom(3), and Z = 4 at -50 degrees C, R-1 = 0.0533, and wR(2) = 0.1158. TcO2F3. XeO2F2 crystallizes in the orthorhombic system Cmc2(1), with a = 7.895(2) Angstrom, b = 16.204(3) Angstrom, c = 5.198(1) Angstrom, beta = 90 degrees, V = 665.0(2) Angstrom(3), and Z = 4 at 24 degrees C, R-1 = 0.0402, and wR(2) = 0.0822. The structures of TcO2F3. SbF5 and ReO2F3. SbF5 consist of infinite chains of alternating MO2F4 and SbF6 units in which the bridging fluorine atoms on the antimony are trans to each other. The structure of TcO2F3. XeO2F2 comprises two distinct fluorine-bridged chains, one of TcO2F3 and the other of XeO2F2 bridged by long Tc-F ... Xe contacts. The oxygen atoms of the group 7 metals in the three structures are cis to each other and to two terminal fluorine atoms and trans to the bridging fluorine atoms. The F-19 NMR and Raman spectra of TcO2F3. PnF(5) and ReO2F3. PnF(5) in SbF5 and PnF(5)-acidified HF solvents are consistent with dissociation of the adducts into cis-MO2F2(HF)(2)(+) cations and PnF(6)(-) anions. The energy-minimized geometries of the free MO2F2+ cations and their HF adducts, cis-MO2F2(HF)(2)(+), have been calculated by local density functional theory (LDFT), and the calculated vibrational frequencies have been used as an aid in the assignment of the Raman spectra of the solid MO2F3. PnF(5) adducts and their PnF(5)-acidified HF solutions. In contrast, ReO2F3. SbF5 ionizes in SO2ClF solvent to give the novel Re2O4F5+ cation and Sb2F11- anion. The F-19 NMR spectrum of the cation is consistent with two ReO2F2 units joined by a fluorine bridge in which the oxygen atoms are assumed to lie in the equatorial plane. The [ReO2F2(CH3CN)(2)][SbF6] salt was formed upon dissolution of ReO2F3. SbF5 in CH3CN and was characterized by H-1,C-13, and F-19 NMR and Raman spectroscopies. The ReO2F2(CH3CN)(2)(+) cation is a pseudooctahedral cis-dioxo arrangement in which the CH3CN ligands are trans to the oxygens and the fluorines are trans to each other.