Eight PdII complexes are chemically and structurally characterized by NMR and X-ray diffraction. Their common structural feature is the planar 2,20-bipyridyl ligand (bipy) faced by variously substituted, vertical pyridines (n-Rpy). Dissymmetric Cs 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–Npy bond. The energetic barrier also owns a steric contribution which becomes dominant for 2-Mepy. Methyl bumping locks rotation and loosens Pd–Npy bond, triggering an alternative isomerization pathway.
NMR characterization, dynamics and crystal structure of[2,20-dipyridyl(bis-pyridine) palladium(II)]2+ and related cations
ROTONDO, Archimede;BRUNO, Giuseppe;CUSUMANO, Matteo;ROTONDO, Enrico
2009-01-01
Abstract
Eight PdII complexes are chemically and structurally characterized by NMR and X-ray diffraction. Their common structural feature is the planar 2,20-bipyridyl ligand (bipy) faced by variously substituted, vertical pyridines (n-Rpy). Dissymmetric Cs 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–Npy bond. The energetic barrier also owns a steric contribution which becomes dominant for 2-Mepy. Methyl bumping locks rotation and loosens Pd–Npy bond, triggering an alternative isomerization pathway.Pubblicazioni consigliate
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