Minkwitz Rolf, Schneider Stefan, Kornath Andreas
Anorganische Chemie, Fachbereich Chemie der Universität Dortmund, D-44221 Dortmund, Germany.
Inorg Chem. 1998 Sep 7;37(18):4662-4665. doi: 10.1021/ic971252c.
Phosphorous acid reacts with the superacidic system HF/SbF(5) with formation of HPF(4), water, and oxonium hexafluoroantimonate, which crystallizes as H(5)O(2)(+)SbF(6)(-) in the triclinic space group P&onemacr; with a = 6.492(6) Å, b = 7.469(8) Å, c = 8.095(6) Å, alpha = 116.17(7) degrees, beta = 93.90(7) degrees, and gamma = 112.34(7) degrees, with two formula units per unit cell. The unit cell contains two H(5)O(2)(+) ions of approximate symmetry C(2)(h)() with an intramolecular O.O distance of 2.418(8) or 2.40(1) Å, respectively. The reaction is discussed with regard to the formation of protonated species in various superacidic media. In addition the crystal structure of Me(4)N(+)HPF(5)(-) which is formed by the reaction of HPF(4) with Me(4)N(+)F(-) is reported. The salt crystallizes in the tetragonal space group P4/nmm with a = 8.564(5) Å and c = 5.687(2) Å, with two formula units per unit cell. The P-F distances of P-F(eq) = 1.595(6) Å and P-F(ax) = 1.594(9) Å for the psi-octahedral HPF(5)(-) show no significant interaction exercised by hydrogen on the cis- and trans-fluorine.
亚磷酸与超强酸体系HF/SbF₅反应，生成HPF₄、水和六氟锑酸氧鎓盐，其在三斜空间群P&onemacr;中结晶为H₅O₂⁺SbF₆⁻，a = 6.492(6) Å，b = 7.469(8) Å，c = 8.095(6) Å，α = 116.17(7)°，β = 93.90(7)°，γ = 112.34(7)°，每个晶胞含有两个化学式单元。晶胞包含两个近似具有C₂(h)对称性的H₅O₂⁺离子，其分子内O.O距离分别为2.418(8) Å或2.40(1) Å。讨论了该反应在各种超强酸介质中质子化物种的形成。此外，还报道了HPF₄与Me₄N⁺F⁻反应生成的Me₄N⁺HPF₅⁻的晶体结构。该盐在四方空间群P4/nmm中结晶，a = 8.564(5) Å，c = 5.687(2) Å，每个晶胞含有两个化学式单元。对于ψ-八面体HPF₅⁻，其P-F(eq) = 1.595(6) Å和P-F(ax) = 1.594(9) Å的P-F距离表明氢对顺式和反式氟没有显著相互作用。
