Ruthenium-catalyzed hydrogenation of nitriles: Insights into the mechanism

Article abstract of DOI:10.1021/ja102759z

Hydrogenation of benzonitrile into benzylamine is catalyzed under very mild conditions by the ruthenium bis(dihydrogen) complex RuH₂(H ₂)₂(PCyp₃)₂, incorporating two tricyclopentylphosphines. Two key intermediates have been isolated, resulting from the activation of benzonitrile at early stages of activation, i.e., either N-coordination through the nitrile function or first hydrogenation with benzylimine formation, followed by, thanks to C-H activation, coordination at ruthenium as an orthometalated ligand.