A Ruthenium Hydrido Dinitrogen Core Conserved across Multielectron/Multiproton Changes to the Pincer Ligand Backbone

A series of ruthenium(II) hydrido dinitrogen complexes supported by pincer ligands in different formal oxidation states have been prepared and characterized. Treating a ruthenium dichloride complex supported by the pincer ligand bis(di-tert-butylphosphinoethyl)amine (H-PNP) with reductant or base generates new five-coordinate cis-hydridodinitrogen ruthenium complexes each containing different forms of the pincer ligand. Further ligand transformations provide access to the first isostructural set of complexes featuring all six different forms of the pincer ligand. The conserved cis-hydridodinitrogen structure facilitates characterization of the π-donor, π-acceptor, and/or σ-donor properties of the ligands and assessment of the impact of ligand-centered multielectron/multiproton changes on N₂ activation. Crystallographic studies, infrared spectroscopy, and ¹⁵N NMR spectroscopy indicate that N₂ remains weakly activated in all cases, providing insight into the donor properties of the different pincer ligand states. Ramifications on applications of (pincer)Ru species in catalysis are considered.