Mixed Noble‐Gas Compounds of Krypton(II) and Xenon(VI); [F₅Xe(FKrF)AsF₆] and [F₅Xe(FKrF)₂AsF₆]

Abstract

The coordination chemistry of KrF 2 has been limited in contrast with that of XeF 2 ,w hich exhibits af ar richer coordination chemistry with main-group and transition-metal cations.I nt he present work, reactions of [XeF 5 ][AsF 6 ]w ith KrF 2 in anhydrous HF solvent afforded [F 5 Xe(FKrF)AsF 6 ] and [F 5 Xe(FKrF) 2 AsF 6 ], the first mixed krypton/xenon compounds.X-ray crystal structures and Raman spectra show the KrF 2 ligands and [AsF 6 ] À anions are F-coordinated to the xenon atoms of the [XeF 5 ] + cations.Q uantum-chemical calculations are consistent with essentially noncovalent li-gandÀxenon bonds that may be described in terms of s-hole bonding.These complexes significantly extend the XeF 2-KrF 2 analogy and the limited chemistry of krypton by introducing anew class of coordination compound in whichKrF 2 functions as al igand that coordinates to xenon(VI). The HF solvates, [F 5 Xe(FH)AsF 6 ]and [F 5 Xe(FH)SbF 6 ], are also characterized in this study and they provide rare examples of HF coordinated to xenon(VI).

Boron‐Based Functional Additives Enable Solid Electrolyte Interphase Engineering in Calcium Metal Battery

“…[38] Crystal selection and mounting was carried out at low temperature (about À 50 to À 60 °C) under protective cold nitrogen stream employing a previously described low-temperature crystal mounting procedure. [39] The crystal structures of BF 3 • OC(CH 3 ) 2 and BF 3 • OC(OCH 2 ) 2 measured at 150 K are in good agreement with previously determined structures [24] at 100 K: ], CCDC number: 1972336. [24] BF 3 • OC(CH 3 ) 2 , (P2 1 /n, a = 6.8416(2) Å, b = 14.4962(4) Å, c = 6.9580(2) Å, β = 115.8250(10)°, V = 621.16(3) Å 3 ), CCDC number: 1972338.. [24]…”

“…Hydrogen atoms were freely refined including an isotropic thermal parameter [38] . Crystal selection and mounting was carried out at low temperature (about −50 to −60 °C) under protective cold nitrogen stream employing a previously described low‐temperature crystal mounting procedure [39] …”

Noble‐Gas Difluoride Complexes of MOF4(M=Mo, W); Syntheses, Structures and Bonding of NgF2 ⋅ MOF4and XeF2 ⋅ 2MOF4(Ng=Kr, Xe)

“…[9] The NgÀ F bonds of the NgF 2 ligand become more polarized, consistent with the calculated FIAs of the Group 6 oxide tetrafluorides (CrOF 4 , À 285; MoOF 4 , À 355 WOF 4 , À 386 kJ mol À 1 ), [12] which ). [9] Similar trends have been noted for other terminally coordinated NgF 2 (Ng = Kr, Xe) adducts: [F 2 OBr (FNgF) 2 AsF 6 ], [13,14] [Mg(FKrF) 4 (AsF 6 ) 2 ], [15] [F 5 Xe(FNgF) n AsF 6 ] (n = 1, 2), [16,17] and [Hg(FKrF) 8 ][AsF 6 ] 2 . [18] The MoÀ O (Kr, 1.6508( 12 3) Å) bond lengths are comparable to those of the infinite-chain MoOF 4 [19] and tetrameric WOF 4 structures, [20] and gaseous monomeric MOF 4 (Mo, [21] W [22] ).…”

“…The F−Kr−F bond angles are near‐linear (178.3(2)–179.19(5)°), and are comparable to those of NgF 2 ⋅ CrOF 4 (Kr: 179.91(5)°; Xe: 179.1(1), 179.81(8)°), [9] The Ng−F b ‐ ‐ ‐M bond angles in KrF 2 ⋅ MOF 4 (Mo, 134.33(5); W, 135.22(12)°) and XeF 2 ⋅ MOF 4 (Mo, 148.09(7); W, 150.6(2)°) are bent and are in good agreement with those of NgF 2 ⋅ CrOF 4 (Kr: 123.51(4)°; Xe: 133.1(1), 118.50(8)°) [9] . Similar trends have been noted for other terminally coordinated NgF 2 (Ng=Kr, Xe) adducts: [F 2 OBr(FNgF) 2 AsF 6 ], [13,14] [Mg(FKrF) 4 (AsF 6 ) 2 ], [15] [F 5 Xe(FNgF) n AsF 6 ] ( n =1, 2), [16,17] and [Hg(FKrF) 8 ][AsF 6 ] 2 [18] …”

A new krypton complex – experimental and computational investigation of the krypton sulphur pentafluoride cation, [KrSF5]+, in the gas phase

“…12 Remarkably, mixed noble gas compounds of Kr(II) and Xe(VI) were reported recently, which significantly extend the limited chemistry of krypton. 13 The stabilization of more challenging noble gas species has only been accomplished under low-temperature environments, in high pressure devices, or in the isolated conditions of the gas phase. 1,2,[14][15][16][17][18] Several gas-phase studies were reported over the years involving SF 6 and the noble gases.…”