Dealkylation, isocyanide complexes

It should be noted that the preparation of complexes (RNC)AuCN can be carried out via very special routes. Thus AuCN reacts with Mel to give (MeNC)AuCN. This reaction involves an interesting A-alkylation of an Au(i)-bound cyanide group.219 Other (RNG)AuGN complexes were obtained from the reaction of K[AuC14] with the isocyanide in methanol. Examples are the compounds (L)Au2(CN)2 with L = l,8-diisocyano-/>-menthane or 2,5-diisocyano-2,5-dimethyl-hexane. The reactions proceed with a dealkylation of an isocyanide in the coordination sphere of a gold(m) center to produce free cyanide (Scheme 53).201... 

Another type of complex in which Tc C bonds predominate is the seven-coordinate complex [Tc(CNR)gX] + (398) (R = variety of organic groups X = C1, Br). The compounds are easily prepared in good yield by reaction of the Tc complex [Tc(CNR)6] " with Br2 or CI2 in acetonitrile. Attempts to introduce a bipy ligand as well led to dealkylation of the isocyanide to give the seven-coordinate complex [Tc(CNR)5(CN)X]+ (399). Reductive coupling of the coordinated isocyanides was attempted, but the reduction of Tc to Tc was the only reaction." ... 

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