Electron-rich, bulky PNN-type ruthenium complexes: synthesis, characterization and catalysis of alcohol dehydrogenation.

Reaction of the electron-rich, bulky tridentate PNN ligand (PNN=2-di-tert-butylphosphinomethyl-6-diethylaminomethylpyridine) with Ru(PPh3)3Cl2 at 65 degrees C resulted in formation of the mononuclear dinitrogen complex (PNN)Ru(Cl)2N2 (minor) and the N2 bridged Ru(II) dinuclear complex [(PNN)Ru(Cl)2]2(micro-N2) (major). These complexes can be interconverted; passing argon through a solution of the mixture resulted in formation of pure . The cationic square-pyramidal [(PNN)Ru(PPh3)Cl]OTf was obtained by the reaction of complex with silver triflate followed by PPh3. Reaction of complex with CO yielded (PNN)Ru(CO)Cl2, which upon reaction with one equiv. of AgBF4 gave the cationic [(PNN)Ru(CO)Cl]BF4. The dicationic [(PNN)Ru(CO)(H2O)(acetone)](BF4)2 was obtained from with 2 equiv. of AgBF4 in acetone solution. Complexes , and were structurally characterized by X-ray crystallography. Complexes and upon addition of an equivalent of base, catalyzed the dehydrogenation of secondary alcohols to the corresponding ketones and primary alcohols to esters in good yields and high selectivity accompanied with the evolution of hydrogen gas.