Minkwitz Rolf, Reinemann Stefan, Blecher Oliver, Hartl Hans, Brüdgam Irene
Anorganische Chemie, Fachbereich Chemie der Universität Dortmund, D-44221 Dortmund, Germany, and Institut für Anorganische und Analytische Chemie der Freien Universität Berlin, D-14195 Berlin, Germany.
Inorg Chem. 1999 Mar 8;38(5):844-847. doi: 10.1021/ic981212o.
We have studied the preparation and isolation of the halogenated alkylidene oxonium salts CH(3)OCHX(+)MF(6)(-) (X = Cl, F; M = As, Sb). Addition of dichloromethylmethylether at -78 degrees C to the superacidic media HF/MF(5) resulted in the formation of the chlorine compounds CH(3)OCHCl(+)MF(6)(-), whereas at -65 degrees C the fluorinated salts CH(3)OCHF(+)MF(6)(-) 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 CH(3)OCHF(+)SbF(6)(-) 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) Å; beta = 111.27(2) degrees. The salt CH(3)OCHCl(+)SbF(6)(-) 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) Å; beta = 92.59(3) degrees.
我们研究了卤代亚烷基氧鎓盐CH(3)OCHX(+)MF(6)(-)(X = Cl, F; M = As, Sb)的制备与分离。在-78℃下将二氯甲基甲醚加入到超酸性介质HF/MF(5)中，生成氯化合物CH(3)OCHCl(+)MF(6)(-)，而在-65℃下通过氯/氟交换形成氟化盐CH(3)OCHF(+)MF(6)(-)。这些盐通过低温红外光谱和拉曼光谱进行表征。此外，还给出了六氟锑酸盐的晶体结构。结果表明，阳离子的结构在某些方面有所不同。盐CH(3)OCHF(+)SbF(6)(-)以单斜空间群P2(1)/c结晶，晶胞中有4个分子，a = 9.942(2)，b = 7.454(2)，c = 10.297(3) Å；β = 111.27(2)°。盐CH(3)OCHCl(+)SbF(6)(-)以单斜空间群P2(1)/c结晶，晶胞中有4个化学式单位，a = 5.970(3)，b = 12.019(5)，c = 10.994(5) Å；β = 92.59(3)°。
