The heats of formation of Ni complexes with tetraaza macrocyclic ligands of varying ring size, (12-15 members) were detd. by destroying the complexes in aq. soln. with alk. cyanide. The octahedral-square-planar equil. were investigated, and the results are presented as ΔH° for both octahedral, blue and when possible, square-planar, yellow species. Like the Cu(II) system, the blue, octahedral series exhibits a max. in ΔH° with aneN4. This is discussed in terms of the relative size of the ligand and the metal ion. The unexpected reversal of ΔH° for the 2 square-planar complexes is rationalized in terms of expected ligand transformations.
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