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Synthesis, Characterization and Dynamic Behavior of (π‐Allyl)palladium Complexes with Polydentate Nitrogen Ligands, Evidence of a Dissociative Mechanism
Author(s) -
Elguero José,
Fruchier Alain,
De La Hoz Antonio,
Jalón Félix A.,
Manzano Blanca R.,
Otero Antonio,
GómezDe La Torre Felipe
Publication year - 1996
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19961290519
Subject(s) - chemistry , palladium , denticity , azine , coalescence (physics) , stereochemistry , ketene , medicinal chemistry , photochemistry , organic chemistry , catalysis , metal , physics , astrobiology
New examples of the fluxional behavior of (η 3 ‐allyl)palla‐dium complexes are described. Variable‐temperature experiments and line‐shape analysis of two (η 3 ‐allyl)palladium complexes containing 2‐(1 H ‐pyrazol‐1‐yl)azine ligands were performed in order to determine the activation free energies, enthalpies and entropies of the process. A dissociative mechanism pointing to a selective Pd‐N cleavage is proposed on the basis of these results and NOE experiments above and below the coalescence temperature.