Abstract
The reaction of the saturated polyaza macrocyclic nickel(II) complex [NiL1][ClO4]2(L1= C-meso-3,14-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.07.12] docosane) with concentrated HNO3 in water–methanol (1 : 1) solution yielded the low-spin nickel(III) complex [NiL1(NO3)2]ClO4. The latter is further oxidized in the presence of the acid to produce the diimine complex [NiL2]2+(L2= 3,14-dimethyl-2,6,13,17-tetraazatricyclo-[16.4.0.07.12]docosa-2,13-diene). The monoimine complex [NiL3][ClO4]2(L3= C-meso-3,14-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.07.12] docos-5-ene) can also be prepared by the oxidative dehydrogenation reaction of [NiL1]2+ with HNO3 in water–acetonitrile (1 : 1) solution. The square-planar nickel(II) complexes of L2 and L3 were characterized. The crystal structure of [NiL3][ClO4]2 shows that the complex has a somewhat distorted square-planar geometry.
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