Reactions of functionalised aryl groups sigma-bound to ruthenium(II)

Direct ligand reactions of functionalised sigma-aryl groups coordinated to ruthenium(II) have been developed. The reduction of a sigma-nitrophenyl ligand to a sigma-aminophenyl ligand and subsequent acetylation to form a series of sigma-amidophenyl containing complexes is discussed. An alternative route to sigma-aminophenyl complexes which uses a mercury transmetallation reagent is also reported. The complexes Ru(C6H4NO2-4)Cl(CO)(PPh(3))(2) (1), Ru(C6H4NO2-4)(eta(2)-S2CN[CH3](2))(CO)(PPh(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), Ru(C6H4NHC[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]CH3-4)(eta(2)-O2CCH3)(CO)(PPh(3))(2) (9) have been prepared and characterised 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) Angstrom, alpha = 75.78(3), beta = 85.17(2), gamma = 65.06(3)degrees, triclinic, space group <P(1)over bar>, Z = 2; 9, C47H41NO4P2Ru, a = 9.752(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 bar>, Z = 2.