207462-75-7Relevant academic research and scientific papers
Coordinatively saturated fluoro cations. Oxidative fluorination reactions with KrF+ salts and PtF6
Christe, Karl O.,Wilson, William W.,Wilson, Richard D.
, p. 2058 - 2063 (2008/10/08)
The usefulness of KrF+ salts and PtF6 as oxidative fluorinators for the syntheses of the coordinatively saturated complex fluoro cations NF4+, ClF6+, and BrF6+ was studied. The syntheses of NF4SbF6, NF4AsF6, NF4BF4, and NF4TiF5·nTiF4 from KrF2-Lewis acid adducts and NF3 were investigated under different reaction conditions. The fluorination of NF3 by KrF+SbF6- in HF solution was found to proceed quantitatively at temperatures as low as -31°C, indicating an ionic two-electron oxidation mechanism. An improved synthesis of KrF+MF6- (M = As, Sb), Raman data and solubilities in HF, and the existence of a Kr2F3+·nKrF2BF 4- adduct in HF at -40°C are reported. Attempts to fluorinate OF2, CF3NF2, and ClF4O- with KrF+ salts were unsuccessful. Whereas KrF+ is capable of oxidizing NF3, ClF5, and BrF5 to the corresponding complex fluoro cations, PtF6 was shown to be capable of oxidizing only NF3 and ClF5. Since the yield and purity of the NF4+ fluoroplatinate salts obtained in this manner were low, NF4PtF6 was also prepared from NF3, F2, and PtF6 at elevated temperature and pressure. General aspects of the formation mechanisms of coordinatively saturated complex fluoro cations are discussed briefly.
