Abstract
This paper describes the synthesis and characterization of heteropolynuclear redox active materials [FerCuCl]^sub 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^sub 2^ uptake measurements in PhNO^sub 2^ show that tetranuclear [FerCuCl]^sub 4^ and [FerCuCl]^sub 4^Cat give the tetranuclear oxocopper(II) products [FerCuCl]^sub 4^O^sub 2^ and [FerCuCl]^sub 4^CatO, respectively. The absence of carbonyl stretching vibrational bands in [FerCuCl]^sub 4^Cat^sub 2^ and [FerCuCl]^sub 4^CatO suggest that tetrachloro-1,2-benzoquinone (TClBQ) is reduced to the corresponding catecholete during the oxidation of copper(I) centers in [FerCuCl]^sub 4^. The near i.r. electronic spectra for [FerCuCl]^sub 4^O^sub 2^, [FerCuCl]^sub 4^CatO and [FerCuCl]^sub 4^Cat^sub 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]^sub 4^CatO and [FerCuCl]^sub 4^Cat^sub 2^ are of the axial type, suggesting a square pyramidal geometry around Cu^sup II^.[PUBLICATION ABSTRACT]