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Ambident Reactivity of the Cyanide Ion: A Failure of the HSAB Principle
Author(s) -
Tishkov Alexander A.,
Mayr Herbert
Publication year - 2004
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200461640
Subject(s) - hsab theory , reactivity (psychology) , chemistry , nucleophile , carbocation , observable , cyanide , cyanide ion , ion , diffusion , medicinal chemistry , computational chemistry , organic chemistry , thermodynamics , physics , quantum mechanics , catalysis , medicine , alternative medicine , pathology
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.