• Bulletin of the Korean Chemical Society
• /
• v.35 no.7
• /
• pp.2043-2048
• /
• 2014

Two isomers of a new tetraaza macrotricycle 2,2,4,9,9,11-hexaazamethyl-1,5,8,12-tetraazatricyclo[$10.2.2^{5.8}$]-octadecane ($L^2$) containing additional N-$CH_2CH_2$-N linkages, C-meso-$L^2$ and C-racemic-$L^2$, have been prepared by the reaction of 1-bromo-2-chloroethane with C-meso-$L^1$ or C-racemic-$L^1$ ($L^1$ = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). Both C-meso-$L^2$ and C-racemic-$L^2$ react with copper(II) ion to form $[Cu(C-meso-L^2)]^{2+}$ or $[Cu(C-racemic-L^2)]^{2+}$ in dehydrated ethanol, but do not with nickel(II) ion under similar conditions. Crystal structure of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ shows that the complex has distorted square-pyramidal coordination geometry with an apically coordinated water molecule. Unexpectedly, the Cu-N distances [2.016(3)-2.030(3) ${\AA}$] of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ are longer than those [1.992(3)-2.000(3) ${\AA}$] of [Cu(C-racemic-$L^1$)($H_2O$)]$(ClO_4)_2$. As a result, $[Cu(C-racemic-L^2)(H_2O)]^{2+}$ exhibits weaker ligand field strength than $[Cu(C-racemic-L^1)(H_2O)]^{2+}$. The copper(II) complexes readily react with CN- ion to yield the cyano-bridged dinuclear complex $[Cu_2(C-meso-L^2)_2CN]^{3+}$ or $[Cu_2(C-racemic-L^2)_2CN]^{3+}$. Spectra and chemical properties of $[Cu(C-meso-L^2)]^{2+}$ and $[Cu_2(C-meso-L^2)_2CN]^{3+}$ are not quite different from those of $[Cu(C-racemic-L^2)]^{2+}$ and $[Cu_2(C-racemic-L^2)_2CN]^{3+}$, respectively.

• Journal of the Korean Chemical Society
• /
• v.35 no.5
• /
• pp.527-533
• /
• 1991

Template condensation reactions of formaldehyde with appropriate tetramines and diamines in the presence of N(II) or Cu(II) ion produce square planar complexes of hexaaza macrotricyclic and macrotetracyclic ligands $[M(L)]^{2+}$(M = Ni(II) or Cu(II); L = 4-methyl-1,3,6,8,11,14-hexaazatricyclo[12,2,1,$1^{8,11}$]octadecane(C), 1,3,10,12,15,18-hexaazatetracyclo[16,2,1,$1^{12,15},0^{4,9}]$docosane(D) 4-methyl-1,3,6,8,12,15-hexaazatricyclo[13,3,1,$1^{8,12}$]eicosane(F), or 1,3,10,12,16,19-hexaazatetracyclo[l7,3,1,$1^{12,16},0^{4,9}]$tetracosane(G). These complexes contain two 1,3-diazacyclopentane or 1,3-diazacyclohexane rings in the six-membered chelate rings. The complexes of C and F contain one methyl group and those of D and G one cyclohexane ring in the five-membered chelate ring. Synthesis and characterization of the Ni(II) and Cu(II) complexes are presented. The effects of the ligand structure on the equilibrium $[Ni(L)]^{2+}2H_2O{\rightleftharpoons}[Ni(L)(H_2O)_2]^{2+}$ in aqueous solutions are described.