Wiley, European Journal of Inorganic Chemistry, 22-23(2013), p. 4077-4084, 2013
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The complexes (Bu4N)(LMeM(II)-OH) (LMe = 2,6-dimethylphenyl-substituted pyridine(dicarboxamide); M = Cu or Ni) react with CH3CN to yield (Bu4N)(LMeM-CH2CN), novel cyanomethide complexes that were fully characterized, including by X-ray crystallography. These conversions contrast with the usual reactions of metal-hydroxide complexes with nitriles, which typically involve attack at the nitrile carbon and formation of amides or carboxylic acids. Kinetic studies (M = Cu) revealed a first-order dependence on the complex and a kinetic isotope effect (k(CH3CN)/k(CD3CN) of 4. Various mechanisms involving either intra- or intermolecular deprotonation steps are proposed.