Donor Strength Determination of Pyridinylidene-amide Ligands using Their Palladium-NHC Complexes.

Pyridinylidene-amides (PYAs) are a relatively new type of N-donor ligands that can exist in three isomeric forms and adopt various resonance structures. This makes them electronically flexible, and in order to evaluate their electronic profile using the Huynh electronic parameter (HEP), seven structurally diverse mixed N-heterocyclic carbenes (NHCs)/PYA palladium complexes of the type trans-[PdBr2(iPr2-bimy)(PYA)] were prepared and fully characterized by various spectroscopic and spectrometric methods. This study shows that PYAs are among the strongest, formally neutral N-donors, but they are still weaker than phosphines and organometallic ligands such as NHCs. Notably, the donating abilities of isomeric PYAs are distinct and can be further fine-tuned by the choice of two substituents making them structurally and electronically versatile. These characteristics and the ease of their preparation hold promise for a wide applicability in coordination chemistry.