Fluorine bridging in the xenon fluoride cations and their salts: The base strengths of XeF2, XeF4 and XeF6

Synthesis, Structure, and Bonding of a XeIV Transition‐Metal Coordination Complex, F3XeFb‐ ‐ ‐WOF4

“…The Wiberg bond index of W---F b (0.097) is somewhat less than the W---F b bond indices of FNgF b ---WOF 4 (Xe, 0.117; Kr, 0.110) and consistent with the lower fluorobasicity of XeF 4 relative to NgF 2 . [1] In the MEPS analysis (Figure 2), the electrostatic potential (EP) minima of the F atoms of XeF 4 (À 34 kJ mol À 1 ) are significantly less negative than those of NgF 2 (Xe, À 78 kJ mol À 1 ; [9] Kr, À 64 kJ mol À 1 [9] ), in accordance with the higher formal oxidation state of Xe IV and the lower fluorobasicity of XeF 4 .…”

“…Xenon tetrafluoride is the weakest fluoride‐ion donor among the binary noble‐gas fluorides (relative fluoride‐ion donor strengths: XeF 6 >XeF 2 ≈KrF 2 ≫XeF 4 ) [1, 2] and a powerful oxidative fluorinating agent [2] . The reactions of XeF 4 with the strong fluoride‐ion acceptors, liquid SbF 5 or SbF 5 and BiF 5 in anhydrous HF (aHF) solvent, result in intimately ion‐paired [XeF 3 ][Pn n F 5 n +1 ] ( n =1, 2; Pn=Sb, Bi) salts [2] .…”

“…[14] The W---F b bond (2.239(5) Å) is primarily electrostatic and is best described as a σ-hole bond that is longer and somewhat weaker than the W---F b bonds of FNgF b ---WOF 4 (Kr, 2.217(2); Xe, 2.199(3) Å), [9] in accordance with the lower fluorobasicity of XeF 4 relative to NgF 2 . [1] The bent W---F b À Xe bond angle (145.2(2)°) indicates that the W---F b bond has a degree of covalent character (vide infra).…”

Synthesis, Structure, and Bonding of a XeIV Transition‐Metal Coordination Complex, F3XeFb‐ ‐ ‐WOF4

“…Zuschriften is somewhat less than the W---F b bond indices of FNgF b ---WOF 4 (Xe, 0.117; Kr, 0.110) and consistent with the lower fluorobasicity of XeF 4 relative to NgF 2 . [1] In the MEPS analysis (Figure 2), the electrostatic potential (EP) minima of the F atoms of XeF 4 (À 34 kJ mol À 1 ) are significantly less negative than those of NgF 2 (Xe, À 78 kJ mol À 1 ; [9] Kr, À 64 kJ mol À 1 [9] ), in accordance with the higher formal oxidation state of Xe IV and the lower fluorobasicity of XeF 4 .…”

Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF5]+ and [Xe2F11]+ Salts of the [CrVIOF5]−, [CrVOF5]2−, [CrV2O2F8]2−, and [CrIVF6]2− Anions

“…[12,[47][48][49] Instead, NgF 2 coordinates to the metal by meanso fN g-F---M bridges. [12] Xenon hexafluoridei sm ore fluorobasic than XeF 2 , [50] and is, therefore, more likely to donate fluoridei on to CrOF 4 to [51] Ap rior attemptt os ynthesize aC r V fluoro-anions alt by use of XeF 6 as af luoridei on donor led to Cr V reduction andF 2 elimination. [52] Instead of the anticipated [XeF 5 ][Cr V F 6 ]s alt, the reactiono fX eF 6 with CrF 5 yielded [XeF 5 ][Cr IV F 5 ], whichw as characterized by single-crystal X-ray diffraction [Eq.…”