Syntheses and characterization of η6-hexamethylbenzeneruthenium(II)-β-diketone complexes: their reactions with mono- and bidentate neutral ligands

The complex [(η6-C6Me6)Ru(μ-Cl)Cl]21 react with sodium salts of β-diketonato ligands in methanol to afford the oxygen bonded neutral complexes of the type [(η6-C6Me6)Ru(κ2-O,O ′-R1COCHCOR2)Cl] {R1, R2 = CH3 (2), CH3, C6H5 (3), C6H5 (4), OCH3 (5), OC2H5 (6)}. Complex 4 with AgBF4 yields the γ-carbon bonded ruthenium dimeric complex 7. Complex 4 also reacts with tertiary phosphines and bridging ligands to yield complexes of the type [(η6-C6Me6)Ru(κ2-O,O ′-C6H5COCHCOC6H5)(L)]+ (L = PPh3 (8), PMe2Ph (9)) and [{η6-C6Me6)Ru(κ2-O,O ′-C6H5COCHCOC6H5)}2(μ-L)] L = 4,4′-bipyridine (4,4′-bipy) (11), 1,4-dicyanobenzene (DCB) (12) and pyrazine (Pz) (13). Complexes 2–4 react with sodium azide to yield neutral complexes [(η6-C6Me6)Ru(κ2-O,O ′-R1COCHCOR2)N3] {R1, R2 = CH3 (10a), CH3, C6H5 (10b), C6H5 (10c). All these complexes were characterized by FT-IR and FT-NMR spectroscopy as well as analytical data. The molecular structures of complexes [(η6-C6Me6)Ru(κ2-O,O ′CH3COCH–COC6H5)Cl] (3) and [(η6-C6Me6)Ru(κ2-O,O ′-C6H5COCHCOC6H5] (4) were established by single crystal X-ray diffraction studies. The complex 3 crystallizes in the triclinic space group, View the MathML sourceP1¯ [a = 7.9517(4), b = 9.0582(4) and c = 14.2373(8) Å, α = 88.442(3)°, β = 76.6.8(3)° and γ = 81.715(3)°. V = 987.17(9) Å3, Z = 2]. Complex 4 crystallizes in the monoclinic space group, P21/c [a = 7.5894(8), b = 20.708(2) and c = 29.208(3) Å,β = 92.059(3)° V = 4587.5(9) Å3, Z = 8].