Synthesis and reactivity of η6-arene ruthenium anilide complexes

Article abstract of DOI:10.1016/S0277-5387(97)00373-2

The compounds, (η⁶-C₆Me₆)Ru(PMe ₃)(R)(NR′R″) ; (R=Ph, R′=H, R″=Ph, 3 ; R=Me, R′=H, R″=Ph, 4 ; R=Ph, R′=H, R″=p-tol, 5 ; R=Me, R′=Me, R″=Ph, 6) are synthesized through the interaction of (η⁶-C₆Me₆)Ru(PMe₃)(R)(I) and the corresponding anilide salt, KNR′R″ in THF at low temperature. The reactions between these complexes and the unsaturated electrophilic reagents, CO₂ and dimethylacetylene dicarboxylate (DMAD) have been described. The typical reaction involves net insertion of the electrophile into the Ru anilide bond. Complex 6 reacts with H₂O giving the hydroxide complex, 11, which reacts with CO₂ giving the bicarbonato complex, 12. The X-ray crystal structure of 3 is reported. Compound 3 crystallizes in the monoclinic space group, P2₁/n, a = 12.013(2) A, b = 16.700(3) A, c = 12.414(1) A, β = 97.35(2), V = 2470.0(7) A³ and Z = 4.