Frank N. Penkert, T. Weyhermüller, E. Bill
Sep 22, 2000
Citations
0
Influential Citations
65
Citations
Journal
Journal of the American Chemical Society
Abstract
The pendent arm macrocyclic aniline ligands 1-(2-amino-3,5-di-tert-butylbenzyl)-4,7-dimethyl-1,4,7-triazacyclononane, H[L1], and 1,4,7-tris(2-amino-3,5-di-tert-butylbenzyl)-1,4,7-triazacyclononane, H3[L2], have been synthesized. The reaction of these ligands in methanol (1:1) and/or ethanol with CoII(ClO4)2·6H2O and potassium di-tert-butylacetylacetonate (1:1) or MnII(acetate)2·4H2O in the presence of air produced the anilido complexes [CoIII(L1)(Bu2acac)](ClO4) (1) and [MnIV(L2)]X (X = ClO4 (2), BPh4 (2‘)), respectively. The reaction of H3[L2] and CuCl2·2H2O in ethanol produced upon addition of NaClO4 blue crystals of [CuII(H3L2)Cl](ClO4) (3) containing two coordinated and one uncoordinated aniline pendent arm. Complexes 1, 2, and 3 have been structurally characterized by X-ray crystallography. Electrochemically, 1 is reversibly oxidized with formation of the paramagnetic anilino radical species [CoIII(L1•)(Bu2acac)]2+ (S = 1/2) whereas the cyclic voltammogram of 2 displays three ligand-centered one-elec...