?Almost every element in the periodic table has well-defined halide chemistry. Technetium, the first radioelement, is a notable exception. Prior to 2008, only 3 binary halides of technetium had been reported, viz., TcF6, TcF5 and TcCl4. These compounds were prepared almost 60 years ago from the reactions of the metal with F2 or Cl2. Since 2008, a team of scientists at Argonne, UNLV and Northwestern has synthesized and characterized an additional 6 binary halides, including two polymorphs of TcCl3, TcCl2, TcBr4, TcBr3 and TcI3, and several related cluster compounds. These new halides can be binned into one of three categories: (1) those that have molybdenum and/or ruthenium analogues, (2) those that have rhenium analogues, and (3) those for which no analogues with neighboring elements currently exist. The synthetic routes to the new halides and their relationship to molecular technetium systems will be described. Solid-state structures, thermal stabilities, and selected aqueous and non-aqueous chemistry will be discussed. The synthesis of these new halide compounds opens up exciting new opportunities for exploring the synthetic and mechanistic chemistry of low-valent technetium, as well as the possibility of new applications for the nuclear fuel cycle.

Connecting the molecular and solid-state chemistry of technetium

247th National Meeting (2014)

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