Nickel(II), palladium(II), and platinum(II) complexes of meso-aryl-substituted [26]hexaphyrin have been prepared and structurally characterized. In mono-metalated complexes, the metal ion is commonly bound with three pyrrolic nitrogen atoms and one pyrrolic beta-carbon, whereas a bis-Pd(II) complex exhibits a unique structure involving a Pd-C(alpha) bond. These results reveal novel coordination abilities of the hexaphyrin that lead to a metal-carbon bond at either pyrrolic C(beta) or C(alpha) position.
The copper metalation into the hexaphyrins is accompanied by large structural changes to give four complexes exhibiting gable structures and varying antiferromagnetic couplings.
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