Synthesis and reactivity of η6-arene ruthenium anilide complexes

The compounds, (eta(6)-C6Me6)Ru(PMe3)(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 (eta(6)-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, P2(1)/n, a = 12.013(2) Angstrom, b = 16.700(3) Angstrom, c = 12.414(1) Angstrom, beta = 97.35(2), V = 2470.0(7) Angstrom(3) and Z = 4. (C) 1998 Elsevier Science Ltd. All rights reserved.