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(NH4)2[Tc2O2(S2O7)4]: An Unexpected Technetium(V)-Sulfate From the Reaction of (NH4)(TcO4) With SO3
Stefan Sutorius1, Julian Heinen2, David van Gerven1
1Institute of Inorganic Chemistry, University of Cologne, Cologne, Germany.
Abstract:
The reaction of ammonium pertechnetate, (NH4)(TcO4), with SO3 leads to crystals of (NH4)2[Tc2O2(S2O7)4] (monoclinic, P21/c, Z = 2, a = 775.67(5), b = 1339.55(8), c = 1233.32(8) pm, β = 100.566(2)°). The compound contains the dimeric [Tc2O2(S2O7)4]2- anion with the Tc atom connected by disulfate anions. It is astonishing that even under the oxidizing reaction conditions, reduction of the Tc(VII) starting material occurs. Contrastingly, an analogous reaction of (NH4)(ReO4) with SO3 gives the Re(VII) sulfate (NH4)[ReO2(S2O7)2] (orthorhombic, Pca21, Z = 8, a = 1842.7(1), b = 847.03(5), c = 1663.8(1) pm). The compounds have been further studied by vibrational spectroscopy and quantum mechanical calculations.
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