Metallation of aliphatic carbon atoms. Part 5. Synthesis and characterization of the cyclopalladated complexes of 2-(trimethylsilyl)pyridine and their dynamic behaviour observed by proton nuclear magnetic resonance spectroscopy

Abstract
2-(Trimethylsilyl)pyridine reacts with palladium(II) acetate in benzene at 47 °C to give an acetato-bridged binuclear cyclopalladated complex [{[graphic omitted])(O2CMe)}2](1). Complex (1) is converted to a chloro-bridged analogue, [{[graphic omitted])Cl}2](2), by metathetical reaction with LiCl·H2O. Each of complexes (1) and (2) is composed of cis and trans isomers, and shows dynamic behaviour in its 1H n.m.r. spectrum. This phenomenon in (1) is ascribed to inversion of the acetato bridges, whereas that of (2) is associated with cis–trans isomerization. Complex (2) undergoes bridge-splitting reactions with triphenylphosphine and 3,5-dimethylpyridine to yield the corresponding mononuclear cyclopalladated complexes. All the cyclopalladated complexes are characterized by means of i.r. and n.m.r. spectroscopy.

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