A three-year program investigating the basic coordination and organometallic chemistry of technetium will be reviewed. This work focused on, what were then, relatively unexplored oxidation states and ligation for technetium. Highlights from over 20 publications involving almost every oxidation state known for technetium will be presented. Novel high-valent chemistry included the first imido and iodo complexes observed for Tc(VII), the first tris(imido)cyclopentadienyl (shown here) complexes for any metal, the first “ethane-like” M<sub>2</sub>E<sub>6</sub> complex, and the first examples of alkyl substitution of an imido ligand in addition to other unusual reactivity of imido ligands due to π-loading. Ground-breaking low-valent technetium chemistry included the preparation and characterization of the first dihydrogen, vinylidene, and carbyne complexes, as well as new complexes containing Tc-Tc multiple bonds and a water-soluble Tc-carbonyl cluster. Finally, an X-ray-absorption spectroscopic study was performed, providing a strong correlation between oxidation state and chemical shift.

Technetium chemistry at Los Alamos National Laboratory in the early 90s

251st National Meeting (2016)

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