Reactions of ketones with coordinated nitriles on β-diketonato ruthenium complexes leading to formation of compounds with new carbon–carbon bonds

The reactions of [Ru(acac)2(CH3CN)2] with four ketones (acetone, ethyl methyl ketone, acetylacetone and monochloroacetone), and the reactions of [Ru(acac)2(C6H5CN)2] with two ketones (acetone and ethyl methyl ketone) yielded six novel compounds of β-ketiminato ruthenium complexes: [Ru(acac)2(mhmk)], [Ru(acac)2(ehmk)], [Ru(acac)2(mAmk)], [Ru(acac)2(mClmk)], Ru(acac)2(mhbk)], and [Ru(acac)2(ehbk)] (mhmk = 4-iminopentane-2-one mono anion, ehmk = 5-iminohexane-3-one mono anion, mAmk = 3-(1-iminoethyl)-2,4-pentanedione mono anion, mClmk = 3-chloro-4-imino-pentane-2-one mono anion, mhbk = 1-phenyl-1-iminobutane-3-one mono anion, ehbk = 1-phenyl-1-iminopentane-3-one mono anion). All the new complexes have been characterized by elemental analyses, 1H NMR, MS and electronic spectral data. Crystal and molecular structures for the six β-ketimine complexes have been solved by single crystal X-ray diffraction studies. A mechanism involving the attack of ketones on the coordinated nitrile has been proposed. The electrochemical redox behavior of the β-ketimine complexes has been elucidated.