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Download fileStructure and Dynamics of Imidazolium- and Pyridinium-Substituted η3‑Cycloheptatrienide-Pd Complexes
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posted on 2014-11-24, 00:00 authored by Christian Jandl, Karl Öfele, Fritz E. Kühn, Wolfgang
A. Herrmann, Alexander PöthigA range of imidazolium- and pyridinium-substituted
η3-cycloheptatrienide-Pd complexes was synthesized
by nucleophilic
attack of different N-donors on cycloheptatrienylidene-Pd complexes.
Their full characterization is reported along with DFT studies of
their formation and special properties. The target compounds represent
the first crystallographically characterized monomeric allyl complexes
of a Pd dihalide. The cationic substituents on the cycloheptatrienide
ring form strong intramolecular H-bonds to one bromide ligand. The
Pd–allyl bond was found to be highly fluxional, showing a continuous
migration of the metal along the seven-membered ring even at low temperatures.
The exchange of one bromide for a weakly coordinating anion yields
dimeric structures and improves the poor solubility of these complexes,
allowing their further synthetic utilization.