Copper cyanide

Copper cyanide is an inorganic compound with the formula CuCN. This off-white solid occurs in two polymorphs; impure samples can be green due to the presence of Cu(II) impurities. The compound is useful as a catalyst, in electroplating copper, and as a reagent in the preparation of nitriles.

Preparation

Cuprous cyanide is commercially available and is supplied as the low-temperature polymorph. It can be prepared by the reduction of copper(II) sulfate with sodium bisulfite at 60 °C, followed by the addition of sodium cyanide to precipitate pure LT-CuCN as a pale yellow powder.

2 CuSO4 + NaHSO3 + H2O + 2 NaCN → 2 CuCN + 3 NaHSO4

On addition of sodium bisulfite the copper sulfate solution turns from blue to green, at which point the sodium cyanide is added. The reaction is performed under mildly acidic conditions. Copper cyanide has historically been prepared by treating copper(II) sulfate with sodium cyanide, in this redox reaction, copper(I) cyanide forms together with cyanogen:

2 CuSO4 + 4 NaCN → 2 CuCN + (CN)2 + 2 Na2SO4

Because this synthetic route produces cyanogen, uses two equivalents of sodium cyanide per equivalent of CuCN made and the resulting copper cyanide is impure it is not the industrial production method. The similarity of this reaction to that between copper sulfate and sodium iodide to form copper(I) iodide is one example of cyanide ions acting as a pseudo halide. It also explains why copper(II) cyanide, Cu(CN)2, has not been synthesised.
Reactions

Copper cyanide is insoluble in water but rapidly dissolves in solutions containing CN− to form [Cu(CN)3]2− and [Cu(CN)4]3−, which exhibit trigonal planar and tetrahedral coordination geometry, respectively. These complexes contrast with those of silver and gold cyanides, which form [M(CN)2]− ions in solution.[9] The coordination polymer KCu(CN)2 contains [Cu(CN)2]− units, which link together forming helical anionic chains.

Copper cyanide is also soluble in concentrated aqueous ammonia, pyridine and N-methylpyrrolidone.

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