Ambident Reactivity of the Cyanide Ion: A Failure of the HSAB Principle

Abstract

Diffusion or activation control: Free CN− ions are generally alkylated at carbon (see picture). N-attack is only observable in diffusion controlled reactions with carbocations. Since isonitrile formation in reactions with [Ag(CN)2]− is due to the change of the nucleophile, the explanation of these regioselectivities by the hard and soft acids and bases principle has to be abandoned. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2005/z461640_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.