Chlorine monofluoride. Reactions with sulfur oxides

Schack, Carl J.; Wilson, Richard D.

doi:10.1021/ic50084a027

Cited by 36 publications

(8 citation statements)

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“…Methylene chloride- d 2 (D, 99.5%; BDH Chemicals) was dried over CaH 2 powder (99.5%, BDH Chemicals). Sulfuryl chloride fluoride (Allied Chemical, Baker Adamson Division) was purified as previously described . High-purity Ar (99.998%, Air Liquide) or N 2 (obtained from liquid N 2 boil-off and dried by passage through a column of dry 3 Å molecular sieves) gases were used for backfilling reaction and sample vessels.…”

Section: Methodsmentioning

confidence: 99%

Noble-Gas Difluoride Complexes of Mercury(II): The Syntheses and Structures of Hg(OTeF₅)₂·1.5NgF₂ (Ng = Xe, Kr) and Hg(OTeF₅)₂

2014

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The synthesis of high-purity Hg(OTeF5)2 has resulted in its structural characterization in the solid state by Raman spectroscopy and single-crystal X-ray diffraction (XRD) and in solution by (19)F NMR spectroscopy. The crystal structure of Hg(OTeF5)2 (-173 °C) consists of discrete Hg(OTeF5)2 units having gauche-conformations that interact through long Hg---O and Hg---F intramolecular contacts to give a chain structure. The Lewis acidity of Hg(OTeF5)2 toward NgF2 (Ng = Xe, Kr) was investigated in SO2ClF solvent and shown to form stable coordination complexes with NgF2 at -78 °C. Both complexes were characterized by low-temperature Raman spectroscopy (-155 °C) and single-crystal XRD. The complexes are isostructural and are formulated as Hg(OTeF5)2·1.5NgF2. The Hg(OTeF5)2 units of Hg(OTeF5)2·1.5NgF2 also have gauche-conformations and are linked through bridging NgF2 molecules, also resulting in chain structures. These complexes represent the only examples of coordination compounds where NgF2 coordinates to mercury in a neutral covalent compound and the only example of mercury coordinated to KrF2. Moreover, the Hg(OTeF5)2·1.5KrF2 complex is the only KrF2 complex known to contain a bridging KrF2 ligand. Energy-minimized gas-phase geometries and vibrational frequencies for the model compounds, [Hg(OTeF5)2]3 and [Hg(OTeF5)2]3·2NgF2, were obtained and provide good approximations of the local environments of Hg(OTeF5)2 and NgF2 in the crystal structures of Hg(OTeF5)2 and Hg(OTeF5)2·1.5NgF2. Assignments of the Raman spectra of Hg(OTeF5)2 and Hg(OTeF5)2·1.5NgF2 are based on the calculated vibrational frequencies of the model compounds. Natural bond orbital analyses provided the associated bond orders, valencies, and natural population analysis charges.

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Section: Methodsmentioning

confidence: 99%

Noble-Gas Difluoride Complexes of Mercury(II): The Syntheses and Structures of Hg(OTeF₅)₂·1.5NgF₂ (Ng = Xe, Kr) and Hg(OTeF₅)₂

2014

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“…S02C1F was prepared by the interaction of S02 and C1F between -78 °C and room temperature and purified by trap to trap distillation. 32 To ensure that no traces of S02 were present, S02C1F was distilled onto SbFs and then distilled onto dry NaF to remove traces of SbF5 and HF which might be present.…”

Section: Methodsmentioning

confidence: 99%

Xenon-129 pulse Fourier-transform nuclear magnetic resonance spectroscopy

Schrobilgen¹,

Holloway²,

Granger³

et al. 1978

Inorg. Chem.

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High-resolution xenon-129 pulsed Fourier-transform NMR studies have been carried out on a variety of 129Xe-containing compounds. New chemical shift data for this heavy nucleus in a wide range of oxidation states are summarized. The chemical shift range for 129Xe in its compounds exceeds 4000 ppm which is consistent with large paramagnetic contributions to the shielding constant. In lieu of a comprehensive theory of heavy element chemical shifts, empirical correlations among !29Xe chemical shifts are described which provide a sensitive probe for assessing the degree of ionic character in the Xe-F bond.

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“…Existing syntheses of the compound involve the action of fluoride salts on sulfuryl chloride [31], treatment of potassium fluorosulfite with chlorine [32], the reaction of hydrogen fluoride, chlorine and sulfur dioxide with potassium bifluoride supported on charcoal [33], or the reaction of nitrogen trifluoride with sulfuryl chloride [34]. Also, Schack and Wilson have reported the preparation of SO2C1F from chlorine monofluoride and sulfur dioxide at low temperature [35]. None of these methods is as convenient as the reaction of pyridinium poly(hydrogen fluoride) with sulfuryl chloride, which proceeds efficiently and smoothly under mild conditions [25].…”

Section: Preparation Of Sulfur Tetra Fluoride [25]mentioning

confidence: 99%

Fluorine-Containing Reagents in Organic Synthesis

OLAH

Shih

PRAKASH

2003

World Scientific Series in 20th Century Chemistry

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RCH=CHR' or XZ-AgNO3 ^ (RCHXCHFR) -f RCHFCHFR' (X = Br or I) (60-95%)A simple variation of this procedure affords a-fluoro-(3-nitroalkanes: the alkene is added to a solution of nitronium tetrafluoroborate dissolved in pyridinium poly(hydrogen fluoride), a procedure which eliminates the problem of polymerization usually found in reactions conducted in anhydrous hydrogen fluoride [10], e.g. MeCH=CH2 + [NO21+[BF4]--in PPHF McCHFCH2NO2.Reactions with alcohols [9,11 ] Secondary and tertiary alcohols are readily converted to the corresponding fluorides oy pyridinium poly(hydrogen fluoride). With tertiary Across Conventional Lines Downloaded from www.worldscientific.com by PURDUE UNIVERSITY on 04/13/15. For personal use only.

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Chlorine monofluoride. Reactions with sulfur oxides

Cited by 36 publications

References 2 publications

Noble-Gas Difluoride Complexes of Mercury(II): The Syntheses and Structures of Hg(OTeF₅)₂·1.5NgF₂ (Ng = Xe, Kr) and Hg(OTeF₅)₂

Noble-Gas Difluoride Complexes of Mercury(II): The Syntheses and Structures of Hg(OTeF₅)₂·1.5NgF₂ (Ng = Xe, Kr) and Hg(OTeF₅)₂

Xenon-129 pulse Fourier-transform nuclear magnetic resonance spectroscopy

Fluorine-Containing Reagents in Organic Synthesis

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Chlorine monofluoride. Reactions with sulfur oxides

Cited by 36 publications

References 2 publications

Noble-Gas Difluoride Complexes of Mercury(II): The Syntheses and Structures of Hg(OTeF5)2·1.5NgF2 (Ng = Xe, Kr) and Hg(OTeF5)2

Noble-Gas Difluoride Complexes of Mercury(II): The Syntheses and Structures of Hg(OTeF5)2·1.5NgF2 (Ng = Xe, Kr) and Hg(OTeF5)2

Xenon-129 pulse Fourier-transform nuclear magnetic resonance spectroscopy

Fluorine-Containing Reagents in Organic Synthesis

Contact Info

Product

Resources

About

Noble-Gas Difluoride Complexes of Mercury(II): The Syntheses and Structures of Hg(OTeF₅)₂·1.5NgF₂ (Ng = Xe, Kr) and Hg(OTeF₅)₂

Noble-Gas Difluoride Complexes of Mercury(II): The Syntheses and Structures of Hg(OTeF₅)₂·1.5NgF₂ (Ng = Xe, Kr) and Hg(OTeF₅)₂