Syntheses and physicochemical properties of Cu(BF4)2 complexes of polythia[n]ferrocenophanes and the corresponding ferrocenium cations

1,5,9,13-Tetrathia[13]- and 1,5,8,12-tetrathia[12]-ferrocenophanes react with copper(II) tetra-fluoroborate to give 1 : 1 complexes, while 1,5,9-trithia[9]ferrocenophane gives a 2 : 1 complex under the same conditions. Various physicochemical measurements showed that in these complexes the ferrocene nucleus was oxidized to ferrocenium and the copper atom incorporated in the thiamacrocycle was reduced to CuI. The quadrupole splitting values and magnetic moments of the sulphur-substituted ferrocenium cations and their copper(I) complexes showed a good correlation with the Prins parameter of low-symmetry perturbation (x) obtained from e.s.r. measurements.