Syntheses and characterization of η 6-hexamethylbenzeneruthenium(II)-β-diketone complexes: their reactions with mono- and bidentate neutral ligands

Abstract

The complex [(η 6-C 6Me 6)Ru(μ-Cl)Cl] 2 1 react with sodium salts of β-diketonato ligands in methanol to afford the oxygen bonded neutral complexes of the type [(η 6-C 6Me 6)Ru(κ 2- O,O′-R 1COCHCOR 2)Cl] {R 1, R 2 = CH 3 ( 2), CH 3, C 6H 5 ( 3), C 6H 5 ( 4), OCH 3 ( 5), OC 2H 5 ( 6)}. Complex 4 with AgBF 4 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 [(η 6-C 6Me 6)Ru(κ 2- O,O′-C 6H 5COCHCOC 6H 5)(L)] + (L = PPh 3 ( 8), PMe 2Ph ( 9)) and [{η 6-C 6Me 6)Ru(κ 2- O,O′-C 6H 5COCHCOC 6H 5)} 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 [(η 6-C 6Me 6)Ru(κ 2- O,O′-R 1COCHCOR 2)N 3] {R 1, R 2 = CH 3 ( 10a), CH 3, C 6H 5 ( 10b), C 6H 5 ( 10c). All these complexes were characterized by FT-IR and FT-NMR spectroscopy as well as analytical data. The molecular structures of complexes [(η 6-C 6Me 6)Ru(κ 2- O,O′CH 3COCH–COC 6H 5)Cl] ( 3) and [(η 6-C 6Me 6)Ru(κ 2- O,O′-C 6H 5COCHCOC 6H 5] ( 4) were established by single crystal X-ray diffraction studies. The complex 3 crystallizes in the triclinic space group, P 1 ¯ [ 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) Å 3, Z = 2]. Complex 4 crystallizes in the monoclinic space group, P2 1/ c [ a = 7.5894(8), b = 20.708(2) and c = 29.208(3) Å, β = 92.059(3)° V = 4587.5(9) Å 3, Z = 8].