Pentacyanocobaltate Explained

In chemistry, pentacyanocobaltate is the coordination complex with the formula . When crystallized with a quaternary ammonium cation, it can be obtained as a yellow solid. Pentacyanocobaltate attracted attention as an early example of a metal complex that reacts with hydrogen. It contains low-spin cobalt(II), with a doublet ground state.

Synthesis and structure

Aqueous solutions of pentacyanocobaltate are produced by the addition of five or more equivalents of a cyanide salt to a solution of a cobalt(II) salt. Initially this reaction produces insoluble cobalt dicyanide, but this solid dissolves in the presence of the excess cyanide. Pentacyanocobaltate forms within seconds. When prepared using a quaternary ammonium (quat) cyanide, crystals can be obtained with the formula . According to X-ray crystallography, the salt features square pyamidal .[1]

Reactions

Solutions of undergo a variety of reactions. The complex attracted attention in the 1940s for its reactivity toward hydrogen, which is now understood to produce a cobalt hydride:[2]

When allowed to stand as a dilute solution for several minutes, the complex reacts with water to give two Co(III) derivatives:

In concentrated solution, the complex dimerizes:

With benzyl chloride and related alkylating agents, Co(III) alkyls are formed:[3]

References

  1. 10.1021/ic50153a002. Structural Characterization of the Pentacyanocobaltate(II) Anion in the Salt Tris(diethyldiisopropylammonium) Pentacyanocobaltate(II) . 1975 . Brown . Leo D. . Raymond . Kenneth N. . Inorganic Chemistry . 14 . 11 . 2590–2594 .
  2. 10.1080/01614946808064700. Reactions Catalyzed by Pentacyanocobaltate(II) . 1968 . Kwiatek . Jack . Catalysis Reviews . 1 . 37–72 .
  3. 10.1021/ja01031a010. Reactions of Pentacyanocobaltate(II) with Some Organic Halides . 1969 . Chock . Pwen Boon . Halpern . Jack . Journal of the American Chemical Society . 91 . 3 . 582–588 .