화학공학소재연구정보센터
Inorganic Chemistry, Vol.38, No.5, 844-847, 1999
Halogenated carboxonium salts: Preparation and structural analysis
We have studied the preparation and isolation of the halogenated alkylidene oxonium salts CH3OCHX+MF6- (X = Cl, F; M = As, Sb). Addition of dichloromethylmethylether at -78 degrees C to the superacidic media HF/MF5 resulted in the formation of the chlorine compounds CH3OCHCl+MF6-, whereas at -65 degrees C the fluorinated salts CH3OCHF+MF6- are formed by a chlorine/fluorine exchange. The salts are characterized by their low-temperature IR and Raman spectra. Additionally, the crystal structures of the hexafluoroantimonates are presented. The structures of the cations turned out to be different in some points. The salt CH3OCHF+SbF6- crystallizes in the monoclinic space group P2(1)/c with 4 molecules in the unit cell and a = 9.942(2), b = 7.454(2), and c = 10.297(3) Angstrom; beta = 111.27(2)degrees. The salt CH3OCHCl+SbF6-crystallizes in the monoclinic space group P2(1)/c with 4 formula in the unit cell and a = 5.970(3), b = 12.019(5), and c = 10.994(5) Angstrom; beta = 92.59(3)degrees.