Demetallation of a Ni(II) tetraazamacrocyclic complex by cyanoxime resulting in the formation of a stereospecific trinuclear compound [Na(H2O)6]+[NaNi2L6]- (L = NC-C(NO)-C(O)NH2-)

The reaction between the NiA(ClO4)(2) and NaHL2 {where A = 14ane[N-4], the macrocyclic ligands derived from the product of template condensation of 2,6-diacetylpyridine with aliphatic 3,3'-diaminodipropylamine, NH2(CH2)(3)NH(CH2)(3)NH2; and L=2-cyano-2-isonitrosoacetamide anion, ACO(-) (amidecyanoxime, NC-C(NO)-C(O)NH2-)} has led to the formation of a highly unusual trimetallic bis-[fac-(triscyanoximato) nickel(II)] anionic complex anion instead of the expected Ni(II) macrocyclic complex with coordinated cyanoxime ligands. Two equivalent and symmetric trigonal-prismatic NiL3- units are connected to form the [NaNi2L6](-) anion by the presence of a central sodium cation. The latter is located between two NiL3- anions and has an octahedral NaO6 geometry comprised of oxygen atoms of the nitroso group of the cyanoxime ligand. The oxime ligand is planar and adopts a cis-anti configuration in the complex.