Fluorosulfates structure

Unlike its analogue FCIO3 it forms adducts with BF3 and AsFs, possibly by F" donation to give [I03]+[BF4 ] and [I03]+[AsF6]", though the structures have not yet been determined. Alternatively, the coordination number of the central I atom might be increased. SO3 reduces FIO3 to iodyl fluorosulfate ... 

SeF4 also forms an adduct with S03 which has been investigated in the solid state, the molten state, and in solution (81). The results of infrared, Raman, and NMR studies and some conductometric and cryo-scopic measurements can best be interpreted consistently in terms of a polymeric fluorosulfate bridged structure for the solid and the molten compound. There is also evidence for either a cyclic or linear dimer in dilute solutions in nitrobenzene or HS03F (Fig. 4). 

Nitrato complexes, with monodentate nitrate, are very similar to the fluorosulfates. Thus Au(N03)3 and the better characterized salts of [Au(N03)4]- are known. For example reaction of gold with N205 gives [N02]+[Au(N03)4]-, and the structure of K[Au(N03)4] has been determined.513-515... 

Later it was found that the result of reaction of unsaturated compounds with S03 strongly depends on the structure of fluoroolefin. While HFP gives p-sultone in a high yield under the action of pure S03 [173], perfluoroallylbenzene reacts with S03 exothermally to give a mixture of /1-sultone and F-phenyl-propenyl fluorosulfate, but 3,3,3-trifluorotrichloropropene-l or 2,3-dichloro-F-butene-2 reacts with S03, forming allyl fluorosulfates 87 or 88 [175,176] ... 

The molecular structures of S2Or,F2 and S308F2 in the vapor phase have been determined by electron diffraction (177). However, there has been little chemistry reported for any of these compounds, the exception being the formation of a range of fluorosulfates by reaction of S2O5F2 with the oxides and oxide halides of nitrogen in anhydrous CHgCN (178). 

Iodine monobromide, a solid resulting from direct combination of the elements, is endothermic and extensively dissociated in the vapor. It is used instead of Br2 in some industrial processes. Despite the general instability of the BrX compounds, the fluorosulfate (BrOS02F) obtained by treating Br2 with S206F2, is stable to 150°C. Iodine trichloride (IC13) is also formed (like IC1) by treatment of liquid chlorine with the stoichiometric quantity of iodine, or with a deficiency of iodine followed by evaporation of the excess of chlorine. It is a fluffy orange powder, unstable much above room temperature, with a planar dimeric structure (13-VIII). 

In an extensive and critical review of the synthesis and properties of transition metal fluorosulfates and triflates, Aubke, Cader and Mistry [25] state that the only known molecular structure amongst the fluorosulfates is the dimeric Au(S03F)3, the rest being associated solids. 

IR, Raman, and NMR studies of an adduct of SeF4 with SO2 in the solid and molten states are best interpreted as indicating a polymeric fluorosulfate-bridged structure. Adducts formed between SeF4 and alkali metal fluorides have been characterized by vibrational spectroscopy. The observed Raman and IR spectra of CsSeFs indicate an ionic structure involving a square-pyramidal anion of C4 symmetry. 

Protactinium tetrafluoride, like the other actinide tetrafluorides, possesses the 8-coordinate UF4-type of structure (Table III) but no bond distances are available. It is easily the most stable tetravalent halide of protactinium and can be handled in the atmosphere, at least for a limited period, without hydrolysis or oxidation occurring. As mentioned earlier it is the usual starting material for the preparation of protactinium metal. Tetrafluoride hydrates have not been fully characterized, but a mixed fluorosulfate, PaF2S04 2H20 can be precipitated from aqueous solution (131). Protactinium tetrafluoride is soluble in aqueous ammonium fluoride solutions, for which some spectral properties have been recorded (4, 83). 

The Crystal Structure of Xenon(II) Fluoride Fluorosulfate, FXeOSOaF... 

Iodosyl fluorosulfate, OIOSO2F and the triflate, OIOTf, can be prepared as thermally stable, hygroscopic yellow solids by the reaction of iodine with iodine pentoxide or iodic acid in fluorosulfonic or trifluoromethanesulfonic acids, respectively [5]. Raman and infrared spectra of these compounds indicate a polymeric structure analogous to iodosyl sulfate [5], Iodine tris(fluorosulfate), I(0S02F)3 and tris(triflate), I(OTf)3, are also known [6,26]. I(0S02F)3 can be prepared by the reaction of iodine with peroxydisulfuryl ditluoride [26]. Salts such as KI(0S02F)4 have also been prepared and investigated by Raman spectroscopy [26,27]. I(OTf)3 was prepared from iodine tris(trifluoroacetate) and trifluoromethanesulfonic acid [6]. 

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