Reactivity of (Dicarboxamide)M(II)-OH (M = Cu, Ni) Complexes: Reaction with Acetonitrile to Yield M(II)-Cyanomethides.

ABSTRACT: 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. In addition, (Bu4N)(LMeCu-OH) was oxidized by Fc+PF6- to a proposed Cu(III) complex LMeCuOH at low temperature, and comparisons of

SUBMITTER: Tehranchi J 

PROVIDER: S-EPMC3885180 | biostudies-literature | 2013 Aug

REPOSITORIES: biostudies-literature