Mechanistic Insights into Nitrile Activation by Cobalt(III)-Hydroperoxo Intermediates: The Influence of Ligand Basicity.

ABSTRACT: The versatile applications of nitrile have led to the widespread use of nitrile activation in the synthesis of pharmacologically and industrially valuable compounds. We reported the activation of nitriles using mononuclear cobalt(III)-hydroperoxo complexes, [Co^III(Me₃-TPADP)(O₂H)(RCN)]²⁺ [R = Me (2) and Ph (2^Ph)], to form cobalt(III)-peroxyimidato complexes, [Co^III(Me₃-TPADP)(R-C(=NH)O₂)]²⁺ [R = Me (3) and Ph (3^Ph)]. The independence of the rate on the nitrile concentration and the positive Hammett value of 3.2(2) indicated that the reactions occur via an intramolecular nucleophilic attack of the hydroperoxide ligand to the coordinated nitrile carbon ato

SUBMITTER: Son Y 

PROVIDER: S-EPMC10685436 | biostudies-literature | 2023 Nov

REPOSITORIES: biostudies-literature