NMR characterization, dynamics and crystal structure of [2,2′-dipyridyl(bis-pyridine) palladium(II)]2+ and related cations

Abstract Eight Pd II complexes are chemically and structurally characterized by NMR and X-ray diffraction. Their common structural feature is the planar 2,2′-bipyridyl ligand (bipy) faced by variously substituted, vertical pyridines ( n -Rpy). Dissymmetric C s n -Rpy lead, in solution, to syn and anti geometric isomers whose dynamic interconvertion can be either driven by pyridine rotation or reversible dissociation. Activation energy of the rotational motion is for Pd lower than Pt in accord with a weaker double bond character of Pd–N py bond. The energetic barrier also owns a steric contribution which becomes dominant for 2-Mepy. Methyl bumping locks rotation and loosens Pd–N py bond, triggering an alternative isomerization pathway.