MODELS FOR COPPER PROTEINS - COPPER(I) AND COPPER(II) COMPLEXES OF A NOVEL BINUCLEATING TETRAAMINO-TETRATHIOETHER LIGAND

The novel binucleating ligand, )-1,11-diamino-2,3:9,10-dibenzo-4,8-dit hiaundecane (H4L) was prepared and reacted with copper(II) salts in dr y MeOH to yield mixtures of copper(I) and copper(II) complexes with Cl - and ClO4- counter ions. The amine functions on the ligand release pr otons to form copper(I) complexes: (Cu2L)X-2, where X = Cl-, ClO4-. Th e complexes were oxidized to (Cu2L)X-4 with H2O2 in DMF; Cu(NO3)(2) ga ve a different complex, [Cu-2(H4L)(NO3)(2)](NO3)(2), as regards proton releasing ability, coordination and oxidation number. Evidence for th e structures of this new tetraamino-tetrathioether ligand and its copp er complexes is provided by H-1-, C-13-n.m.r., mass, u.v.-vis., i.r. s pectra, elemental analyses, molar conductivities and magnetic moments.