Abstract

Relatively little is known about the chemistry of technetium, especially in its highest oxidation state. At the same time, 99Tc (I=9/2, Q=−0.19 × 10−24cm 2) is one of the more sensitive NMR nuclei (sensitivity relative to the proton is 0.275 at 100% abundance). Pertechnetate, TcO 4 −, the standard for 99Tc NMR spectroscopy, also displays primary isotopic shifts for 17O- and 18O-enriched samples. Technetium-99 NMR has proven an invaluable structural probe in the study of Tc(VII) oxyfluorides. Noble gas fluorides (KrF 2 and XeF 6) have been used to synthesize novel Tc(VII) species from solutions of TcO 3F in anhydrous HF, i.e. Tc 2O 5F 4 and TcO 2F 3. Pertechnetyl fluoride has also been prepared and its fluoride ion donor properties studied in HF solution. Solid TcO 3 +AsF 6 − has been isolated from these solutions and characterized. In addition to 99Tc NMR, compounds have also been studied by 19F and 17O (enriched) NMR spectroscopy.

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