N-Heterocyclic Phosphenium Ligands as Sterically and Electronically-Tunable Isolobal Analogues of Nitrosyls

The coordination chemistry of an N-heterocyclic phosphenium (NHP)-containing bis­(phosphine) pincer ligand has been explored with Pt⁰ and Pd⁰ precursors. Unlike previous compounds featuring monodentate NHP ligands, the resulting NHP Pt and Pd complexes feature pyramidal geometries about the central phosphorus atom, indicative of a stereochemically active lone pair. Structural, spectroscopic, and computational data suggest that the unusual pyramidal NHP geometry results from two-electron reduction of the phosphenium ligand to generate transition metal complexes in which the Pt or Pd centers have been formally oxidized by two electrons. Interconversion between planar and pyramidal NHP geometries can be affected by either coordination/dissociation of a two-electron donor ligand or two-electron redox processes, strongly supporting an isolobal analogy with the linear (NO⁺) and bent (NO^–) variations of nitrosyl ligands. In contrast to nitrosyls, however, these new main group noninnocent ligands are sterically and electronically tunable and are amenable to incorporation into chelating ligands, perhaps representing a new strategy for promoting redox transformations at transition metal complexes.