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This paper describes the synthesis and characterization of heteropolynuclear redox active materials [FerCuCl] 4 YY¢, Y = Y¢ = O, Y = Y¢ = Cat and Y = O, Y¢ = Cat, Fer = N,N-dimethylaminomethylferrocene and Cat = 3,4, 5,6-tetrachlorocatecholato ligand. Manometric O 2 uptake measurements in PhNO 2 show that tetranuclear [FerCuCl] 4 and [FerCuCl] 4 Cat give the tetranuclear oxocopper(II) products [FerCuCl] 4 O 2 and [FerCuCl] 4 CatO, respectively. The absence of carbonyl stretching vibrational bands in [FerCuCl] 4 Cat 2 and [FerCuCl] 4 CatO suggest that tetrachloro-1,2-benzoquinone (TClBQ) is reduced to the corresponding catecholete during the oxidation of copper(I) centers in [FerCuCl] 4 . The near i.r. electronic spectra for [FerCuCl] 4 O 2 , [FerCuCl] 4 CatO and [FerCuCl] 4 Cat 2 exhibit broad intense split maxima in the 750-875 nm range, attributed to a minimum of three halide ligands per Cu. Room temperature solid state e.p.r. spectra for [FerCuCl] 4 CatO and [FerCuCl] 4 Cat 2 are of the axial type, suggesting a square pyramidal geometry around Cu II .

Copper(I) halides react quantitatively with piperidine in dioxygen-free CH 2 Cl 2 or PhNO 2 to form tetranuclear copper(I) complexes [(pip) n CuX] 4 ; n ¼ 1 or 2 and X ¼ Cl or Br. These complexes are very soluble in CH 2 Cl 2 and PhNO 2 and completely reduce tetrachloro1,2-benzoquinone (TClBQ) and O 2 to the 3,4,5,6-tetrachlorocatecholato ligand (Cat) and the oxo form. The stable solid complexes [(pip) n CuX] 4 Cat 2 and [(pip) n CuX] 4 CatO are closely related to the intermediate, bridging l-catecholato complex, which is formed during the mono-oxygenation and oxidation of PhOH by oxytyrosinase. Cryoscopic and analytical data for these complexes indicate that [(pip) n CuX] 4 Cat 2 and [(pip) n CuX] 4 CatO are discrete tetranuclear species. Electronic transition spectra in the near i.r. with high molecular absorptivity are diagnostic for a tetranuclear 'Cu 4 X 4 ' core structure. The electronic transitions are more likely to be due to charge transfer between a minimum of three halo ligands to the copper(II) center. The room temperature e.p.r. spectra of [(pip) n CuX] 4 Cat 2 and [(pip) n CuX] 4 CatO in CH 2 Cl 2 are isotropic with four hyperfine lines. The room temperature solid state e.p.r. spectra of these complexes show an axial spectra with d x 2) y 2 ground state, suggesting a square pyramidal arrangement around copper(II) centers in all n ¼ 1 complexes and an elongated tetragonal octahedral arrangement around copper(II) centers in all n ¼ 2 complexes. Cyclic voltammetry measurements show that they are more likely to be irreversible and show slight quasi-reversibility when X ¼ Br and n ¼ 2. Constant potential electrolysis indicate that the number of electrons consumed are equal to four which will be due to the reduction of four copper(II) species to copper(I).