Cobalt(II), nickel(II), copper(II), and zinc(II) complexes with [3(5)]adamanzane, 1,5,9,13-tetraazabicyclo[7.7.3]nonadecane and [(2.3)(2).2(1)]adamanzane, 1,5,9,12-tetraazabicyclo[7.5.2]hexadecane

Isolation of the free bicyclic tetraamine, [3(5)]adamanzane .H2O (1,5,9,13- tetraazabicyclo[7.7.3]nonadecane .H2O), is reported along with the synthesi s and characterization of a copper(II) complex of the smaller macrocycle [( 2.3)(2).2(1)]-adamanzane (1,5,9,12-tetraazabicyclo[7.5.2]hexadecane) and of three cobalt(II), four nickel(II), one copper(II), and two zinc(II) comple xes with [3(5)]adamanzane. For nine of these compounds (2-8, 10b, and 12) t he single-crystal X-ray structures were determined. The coordination geomet ry around the metal ion is square pyramidal in [Cu([(2.3)(2).2(1)]adz)Br]Cl O4 (2) and trigonal bipyramidal in the isostructural structures [Cu([3(5)]a dz)Br]Br (3), [Ni-([3(5)]adz)Cl]Cl (5), [Ni([3(5)]adz)Br]Br (6), and [Co([3 (5)]adz)Cl]Cl (8). In [Ni([3(5)]adz)(NO3)]NO3 (4) and [Ni([3(5)]-adz)(ClO4) ]ClO4 (7) the coordination geometry around nickel(II) is a distorted octahe dron with the inorganic ligands at cis positions. The coordination polyhedr on around the metal ion in [Co([3(5)]adz)][ZnCl4] (10b) and [Zn([3(5)]adz)] [ZnCl4] (12) is a slightly distorted tetrahedron. Anation equilibrium const ants were determined spectrophotometrically for complexes 2-6 at 25 and 40 degreesC and fall in the region 2-10 M(-1)for the halide complexes and 30-6 5 M(-1)for the nickel(II) nitrate complex (4). Rate constants for the disso ciation of the macrocyclic ligand from the metal ions in 5 M HCl were deter mined for complexes 2, 3, 5, 8, 10, and 12. The reaction rates vary from ha lf-lives at 40 degreesC of 14 min for the dissociation of the Zn([3(5)]adz) (2+) complex (12) to 14-15 months for the Ni([3(5)]adz)Cl+ ion (5).