Noble-Gas Difluoride Complexes of MOF (M=Mo, W); Syntheses, Structures and Bonding of NgF ⋅ MOF and XeF ⋅ 2MOF (Ng=Kr, Xe).

The NgF  ⋅ MOF (Ng=Kr, Xe; M=Mo, W) and XeF  ⋅ 2MOF complexes were synthesized in anhydrous HF (aHF) solvent and melts, respectively. Their single-crystal X-ray diffraction (SCXRD) structures show NgF  ⋅ MOF and XeF  ⋅ 2MOF have F -Ng-F - - -M arrangements, in which the NgF ligands coordinate to MOF through Ng-F - - -M bridges. The XeF ligands of XeF  ⋅ 2MOF also coordinate to F OM-F '- - -M'OF moieties through Xe-F - - -M bridges to form F -Xe-F - - -M(OF )-F '- - -M'OF , where XeF coordinates trans to the M=O bond and F ' coordinates trans to the M'=O bond.

Syntheses, Structures, and Bonding of NgF ⋅CrOF , NgF ⋅2CrOF (Ng=Kr, Xe), and (CrOF ).

The noble-gas difluoride adducts, NgF ⋅CrOF and NgF ⋅2CrOF (Ng=Kr and Xe), have been synthesized and structurally characterized at low temperatures by Raman spectroscopy and single-crystal X-ray diffraction. The low fluoride ion affinity of CrOF renders it incapable of inducing fluoride ion transfer from NgF (Ng=Kr and Xe) to form ion-paired salts of the [NgF] cations having either the [CrOF ] or [Cr O F ] anions. The crystal structures show the NgF ⋅CrOF adducts are comprised of F -Ng-F - - -Cr(O)F structural units in which NgF is weakly coordinated to CrOF by means of a fluorine bridge, F , in which Ng-F is elongated relative to the terminal Ng-F bond.

Coordination of KrF to a Naked Metal Cation, Mg.

Examples of coordination compounds in which KrF functions as a ligand are very rare. In contrast, XeF provides a rich coordination chemistry with a variety of main-group and transition metal cations. The reactions of Mg(AsF ) and KrF in HF or BrF solvent have afforded [Mg(KrF ) (AsF ) ] and [Mg(KrF ) (AsF ) ]⋅2 BrF , respectively, the first examples of a metal cation ligated by KrF .

H(OXeF2)n][AsF6] and [FXe(II)(OXe(IV)F2)n][AsF6] (n = 1, 2): examples of xenon(IV) hydroxide fluoride and oxide fluoride cations and the crystal structures of [F3Xe---FH][Sb2F11] and [H5F4][SbF6]·2[F3Xe---FH][Sb2F11.

The xenon(IV) hydroxide fluoride and oxide fluoride salts, [H(OXeF2)n][AsF6] and [FXe(II)(OXe(IV)F2)n][AsF6] (n = 1, 2), have been synthesized as the natural abundance and the (18)O- and (2)H-enriched salts and structurally characterized by low-temperature Raman spectroscopy. Quantum-chemical calculations have been used to arrive at vibrational assignments. The experimental vibrational frequencies and isotopic shift trends are reproduced by the calculated gas-phase frequencies at several levels of theory.

Synthesis of the missing oxide of xenon, XeO2, and its implications for Earth's missing xenon.

The missing Xe(IV) oxide, XeO(2), has been synthesized at 0 °C by hydrolysis of XeF(4) in water and 2.00 M H(2)SO(4(aq)). Raman spectroscopy and (16/18)O isotopic enrichment studies indicate that XeO(2) possesses an extended structure in which Xe(IV) is oxygen bridged to four neighboring oxygen atoms to give a local square-planar XeO(4) geometry based on an AX(4)E(2) valence shell electron pair repulsion (VSEPR) arrangement.

Xe3OF3(+), a precursor to a noble-gas nitrate; syntheses and structural characterizations of FXeONO2, XeF2·HNO3, and XeF2·N2O4.

Xenon fluoride nitrate has been synthesized by reaction of NO(2)F with [FXeOXeFXeF][AsF(6)] at -50 °C. It was characterized in SO(2)ClF and CH(3)CN solutions by low-temperature (14)N, (19)F, and (129)Xe NMR spectroscopy and in the solid state by low-temperature Raman spectroscopy (-160 °C) and single-crystal X-ray diffraction (-173 °C). The reactions were carried out using natural abundance and (18)O-enriched [FXeOXeFXeF][AsF(6)] and (15)NO(2)F to aid in the vibrational assignments of FXeONO(2) and to establish the likely reaction pathway.

XeOF3(-), an example of an AX3YE2 valence shell electron pair repulsion arrangement; syntheses and structural characterizations of [M][XeOF3] (M = Cs, N(CH3)4).

The XeOF(3)(-) anion has been synthesized as its Cs(+) and N(CH(3))(4)(+) salts and structurally characterized in the solid state by low-temperature Raman spectroscopy and quantum-chemical calculations. Vibrational frequency assignments for [Cs][XeOF(3)] and [N(CH(3))(4)][XeOF(3)] were aided by (18)O enrichment. The calculated anion geometry is based on a square planar AX(3)YE(2) valence-shell electron-pair repulsion arrangement with the longest Xe-F bond trans to the oxygen atom.

XeF(2) coordination to a halogen center; Raman spectra (n = 1, 2) and X-ray crystal structures (n = 2) of [BrOF(2)][AsF(6)].nXeF(2) and [XOF(2)][AsF(6)] (X = Cl, Br).

The syntheses and structural characterizations of the [XOF(2)][AsF(6)] (X = Cl, Br) salts and the XeF(2) adduct-salts, [BrOF(2)][AsF(6)].nXeF(2) (n = 1, 2), are described. Although the [XOF(2)][AsF(6)] salts have been known for some time, their crystal structures had not been reported until the present study.

A rare example of a krypton difluoride coordination compound: [BrOF2][AsF6] x 2 KrF2.

The synthesis of [BrOF(2)][AsF(6)] x 2 KrF(2), its structural characterization, and bonding are described in this study. Although several KrF(2) adducts with transition metal centers have been previously reported, none have been crystallographically characterized. The solid-state Raman spectrum of [BrOF(2)][AsF(6)] x 2 KrF(2) has been assigned with the aid of quantum-chemical calculations.

XeOF2, F2OXeN identical with CCH3, and XeOF2.nHF: rare examples of Xe(IV) oxide fluorides.

The syntheses of XeOF2, F2OXeNCCH3, and XeOF2.nHF and their structural characterizations are described in this study. All three compounds are explosive at temperatures approaching 0 degrees C.