Almost every element in the periodic table has well-defined halogen chemistry. One exception to this generalization is technetium. Prior to 2008, only 3 binary halides of this radioelement had been reported, viz., TcF6, TcF5 and TcCl4, and these compounds were prepared almost 60 years ago from the reactions of the metal with F2 or Cl2. Since 2008, we have synthesized and characterized an additional 6 binary halides, including two polymorphs of TcCl3, TcCl2, TcBr4, TcBr3 and TcBr2. The new halides fall into one of three categories: (1) those that have molybdenum and ruthenium analogs, (2) those that have rhenium analogs, and (3) those for which no analogs with neighboring elements exist. In this talk, we will describe several synthetic routes to the new halides and their relationship to molecular technetium systems where such relationships exist. We will also describe their solid-state structures, their individual thermal stabilities, and their aqueous and non-aqueous chemistry. The synthesis of these new halide compounds opens up new possibilities for exploring the synthetic and mechanistic chemistry of low-valent technetium.

Connecting the molecular and solid state chemistry of technetium

245th National Meeting (2013)

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