Selective Formation of Mononuclear Palladium and Acetonitrile-Bridged Dinuclear Palladium Complexes Containing a Chiral Tridentate Ligand

From the chiral Schiff base tridentate ligand L, unusual acetonitrile-bridged dinuclear palladium complex 1 and organopalladium complex 1' were synthesized selectively by using acetonitrile and ethanol, respectively. The chiral tridentate Schiff base ligand was bound to the palladium metal center with different chelation modes ([ONO] for 1 and [CNO] for 1'). Complex 1 constitutes the first example of dinuclear metal complexes connected only by a bridging acetonitrile, in which an exceptionally short C≡N bond distance [0.945(12) Å] of bridged acetonitrile was observed. To study the influence of a phenyl group attached to an imine, the phenyl-free ligand L was prepared and used. In that case, an acetonitrile bridge was not observed. Theoretical calculation studies supporting the formation of 1 and 1' are favored.