N-H bond activation by palladium(II) and copper(I) complexes featuring a reactive bidentate PN-ligand

The first examples of reactivity at the backbone of a bidentate PN-ligand L1H relevant to N-H activation are described, leading to novel Pd-II and Cu-I amido complexes. Activation of the PN-ligand backbone led to selective dearomatization of the pyridyl ring structure. In the case of Pd-II, the intermediate could be efficiently stabilized using PMe3. Selective N-H bond cleavage of e.g. trifluorosulfonylamide resulted in facile formation of mononuclear metal-amido species 2 and 4, which have been crystallographically characterized. Hydrogen-bonding dimerization is observed in these solid state structures. The results obtained with these structurally versatile and reactive scaffolds likely open up new avenues in cooperative catalysis.