Synthesis and Characterization of Heteropolynuclear Redox Active Materials[FerCuCl]4YY′; Y = Y′ = O, Y = Y′ = Cat and Y = O, Y′ = Cat, Fer = N,N-dimethylaminomethylferrocene and Cat = 3,4,5,6-tetrachlorocatecholato Ligand

Abstract

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 .

A Novel Catenarian Cyano(triphenyl phosphite) Copper(I) Complex: Synthesis, Crystal Structure, Thermal, Voltammetric and Spectral Properties†

“…5 In particular, a few of copper(I) and gold(I) complexes with tertiary phosphine and its derivatives have been synthesized and cauterized, their structural units stack in the solid state to form versatile conformations. 6,7 Also, great attention has been attracted in the synthesis of organic phosphates for their preventable combustibility and novel structure. 8,9 Phosphate anion and its ramification play a very important role in message transition and energy conservation.…”