SYNTHESIS AND CHARACTERIZATION OF COPPER(II) AND NICKEL(II) COMPLEXESOF TETRAAZA MACROCYCLIC LIGANDS CONTAINING ONE C-NITROMETHYL OR C-AMINOMETHYL PENDANT ARM

The square-planar copper(II) complex [Cu(L(2))(])(2+) (L(2) = ,17-tetr aazatricyclo[16.4.0.0(7.12)]docosa-13-ene) containing one C-nitromethy l pendant arm was synthesized by the nuclecophilic addition of deproto nated nitromethane to the diimine complex [Cu(L(1))](2+) (L(1) = etraa zatricyclo[16.4.0.0(7.12)]docosa-2,13-diene). The copper(II) complex o f L(2) is relatively stable against the dissociation of the nitromethy l group even in basic acetonitrile solutions, in contrast to the corre sponding nickel(II) complex. Reduction of the nitro group of [M(L(2))] (2+) (M = Ni-II or Cu-II) produced the square-pyramidal complex [Cu(L( 3))](2+) (L(3) = ,17-tetraazatricyclo[16.4.0.0(7.12)]docosa-13-ene) or the octahedral complex [Ni(L(3)) (H2O)](2+) containing one C-aminomet hyl group, which is coordinated to the metal ion. Synthesis and charac terization of the complexes of L(2) and L(3), together with the effect s of the pendant arms on their properties, are reported.