16941-06-3Relevant articles and documents
Synthesis and characterization of (Z)-[N3NFO]+ and (E)-[N3NFO]+
Wilson, William W.,Haiges, Ralf,Boatz, Jerry A.,Christe, Karl O.
, p. 3023 - 3027 (2008/03/11)
(Figure Presented) A new stable polynitrogen ion: The second known example of a stable nitrogen fluoride oxide ion, [N3NFO]+, was prepared as its [SbF6]- salt and characterized by multinuclear NMR and vibrational spectroscopy and electronic-structure calculations. The cation is planar and exists as two stereoisomers (see picture; N blue, O red, F dark blue).
Seven-coordinated pnicogens. Synthesis and characterization of the SbF72- and BiF72- dianions and a theoretical study of the AsF72- dianion
Drake, Greg W.,Dixon, David A.,Sheehy, Jeffrey A.,Boatz, Jerry A.,Christe, Karl O.
, p. 8392 - 8400 (2007/10/03)
The novel seven-coordinated BiF72- and SbF72- dianions have been prepared and characterized. The Cs2BiF7, Rb2BiF7, K2BiF7, and Na2BiF7 salts were obtained in high yield by heating BiF5 with an excess of the corresponding alkali metal fluorides to about 250 °C. Attempts failed to prepare the corresponding BiF83- salts or Li2BiF7 under similar conditions. The [N(CH3)4]2BiF7 salt was obtained by the combination of excess N(CH3)4F with BiF5 in CH3CN solution at -31 °C. The (NO2)2BiF7 salt was prepared from BiF5 and a large excess of liquid FNO at -78 °C and decomposes at room temperature to NOBiF6 and FNO. The corresponding Cs2SbF7, K2SbF7, and [N(CH3)4]2SbF7 salts were also synthesized in a similar fashion, but Na2SbF7 was not formed. The pronounced fluoride ion affinity of SbF6- was further demonstrated by the formation of some Cs2SbF7 when dry CsF and CsSbF6 were ball-milled at room temperature. The BiF72- and SbF72- anions, which are the first examples of binary pnicogen compounds with coordination numbers in excess of six, were characterized by vibrational spectroscopy and ab initio electronic structure calculations. They possess pentagonal bipyramidal, highly fluxional structures of D(5h) symmetry, similar to those of IF7 and TeF7-, which are isoelectronic with SbF72-. Although our theoretical calculations indicate that AsF72- is also vibrationally stable, experiments to prepare this dianion were unsuccessful.
Synthesis and properties of NF4+ClO4- and NF4+HF2-·nHF and some reaction chemistry of NF4+ salts
Christe, Karl O.,Wilson, William W.,Wilson, Richard D.
, p. 1494 - 1498 (2008/10/08)
The possibility of synthesizing NF4+XO4- (X = Cl, Br, I) salts by metathesis between NF4SbF6 and CsXO4 in anhydrous HF solution at -78°C was studied. Of these NF4XO4 salts, NF4ClO4 was isolated and characterized by vibrational and 19F NMR spectroscopy. It is an unstable white solid decomposing at 25°C to give NF3 and FOClO3 in high yield. The NF4BrO4 salt is of marginal stability in HF solution and decomposes to NF3, O2, and FBrO2. Attempts to isolate NF4BrO4 as a solid resulted in explosions. The NF4IO4 salt could not be prepared due to the facile fluorination of IO4- to IF4O2- by either HF or BrF5. Attempts to prepare NF4+XF4O- (X = Cl, Br) salts by metathesis between NF4SbF6 and CsXF4O in BrF5 solution at 25°C were unsuccessful; with BrF4O-, fluoride abstraction occurred, resulting in the formation of NF3, F2, and BrF3O, whereas CsClF4O underwent a displacement reaction with BrF5 to give CsBrF6 and ClF3O. The metathetical synthesis of NF4NO3 could not be studied in HF due to the reaction of NO3- with HF to give NO2+, H2O, and HF2-. The metathesis between NF4SbF6 and CsF in HF at -78°C did not produce NF4+F- but produced an unstable white solid of the composition NF4+HF2-·nHF. The composition, thermal stability, spectroscopic properties, and decomposition products of this solid were studied. The NF4+HF2- salt is stable in HF solution at 25°C, and the synthetic usefulness of these solutions for the synthesis of other NF4+ salts is briefly discussed. Attempts to prepare NCl4+ and NCl2O+ salts by F-Cl exchange between BCl3 and NF4+ and NF2O+ were unsuccessful.
