REACTIONS OF FUNCTIONALIZED ARYL GROUPS SIGMA-BOUND TO RUTHENIUM(II)

Direct ligand reactions of functionalised sigma-aryl groups coordinate d to ruthenium(II) have been developed. The reduction of a sigma-nitro phenyl ligand to a sigma-aminophenyl ligand and subsequent acetylation to form a series of sigma-amidophenyl containing complexes is discuss ed. An alternative route to sigma-aminophenyl complexes which uses a m ercury transmetallation reagent is also reported. The complexes Ru(C6H 4NO2-4)Cl(CO)(PPh(3))(2) (1), Ru(C6H4NO2-4)(eta(2)-S2CN[CH3](2))(CO)(P Ph(3))(2) (2), Ru(C6H4NH2-4)Cl(CO)(dmf)(PPh(3))(2) (3), Ru(C6H4NH2-4)( eta(2)-S2CN[CH3](2))(CO)(PPh(3))(2) (4), Ru(C6H4NH2-4)(eta(2)-O2CCH3)( CO)(PPh(3))(2) (5), Ru(C6H4NHC[O]CH3-4)(eta(2)-S2CN[CH3](2)) (6), 4NHC [O]C6H4-4)(eta(2)-S2CN[CH3](2))(CO)(PPh(3))(2) (7), 2,6-[Ru(C6H4NHC[O] -4)(eta(2)-S2CN[CH3](2)) (CO)(PPh(3))(2)]2C5H3N (8) and Ru(C6H4NHC[O]C H3-4)(eta(2)-O2CCH3)(CO)(PPh(3))(2) (9) have been prepared and charact erised using IR and H-1 NMR spectroscopy. The crystal structures of 5 and 9 have been determined by X-ray diffraction methods. Crystal data: 5, C45H39NO3P2Ru . H2O, a = 9.955(2), b = 11.607(3), c = 19.175(7) An gstrom, alpha = 75.78(3), beta = 85.17(2), gamma = 65.06(3)degrees, tr iclinic, space group <P(1)over bar>, Z = 2; 9, C47H41NO4P2Ru, a = 9.75 2(1), b = 11.398(6), c = 19.447(3) Angstrom, alpha = 83.24(2), beta = 86.40(1), gamma = 68.19(3)degrees, triclinic, space group <P(1)over ba r>, Z = 2.