Migratory insertion of hydrogen isocyanide in the pentacyano(methyl)cobaltate(III) anion

The preparation of the pentacyano(iminiumacetyl)cobaltate(III) anion and its N-methyl and N,N-dimethyl derivatives is reported. The iminiumacetyl group is formed by migratory insertion of cis hydrogen isocyanide in the pentacyano(methyl)cobaltate(III) anion. The new compounds have been spectroscopically characterized by (1)H, (13)C, (15)N, and (59)Co NMR spectroscopy and by absorption spectroscopy. The iminium carbon atoms yield (13)C NMR signals at 256.7, 247.7, and 240.4 ppm for the parent iminiumacetyl compound and its N-methyl and N,N-dimethyl derivatives, respectively. The (15)N resonance frequencies of the iminium groups and the lack of rotation of the carbon-nitrogen bond both show that this bond is best described as a double bond. The structure of (Et(4)N)(Ph(4)As)(2)[Co(CN)(5)(CH(3))] was determined by X-ray crystallography at 122.0(5) K. The structure displays disorder.