Polyferrocenylene persulfides, [(BuC{sub 5}H{sub 3})(C{sub 5}H{sub 4})FeS{sub 2}]n, have been prepared by desulfurization of butyltrithiaferrocenophane (BuC{sub 5}H{sub 3})(C{sub 5}H{sub 4})FeS{sub 3}. The molecular precursor was prepared by dilithiation of butylferrocene followed by treatment with elemental sulfur and isolated as a 7:1 mixture of the 1,3,1{prime} and 1,2,1{prime} isomers. The trisulfide was converted to polymer by treatment with the desulfurization agent PBu{sub 3}. The rate of this desulfurization and the nature of the polymer depends critically on the reaction solvent. Desulfurization in DMF and THF afforded insoluble but swellable rubbers. Desulfurization of BufcS{sub 3} in mixed CH{sub 2}Cl{sub 2}-THF solutions gave soluble polymers with M{sub n}, ranging from 12000 to 359000, with lower molecular weight products being favored at high [CH{sub 2}Cl{sub 2}]. The effect of high [CH{sub 2}- Cl{sub 2}] was modeled by the reaction of [fcS{sub 2}]n with a CH{sub 2}Cl{sub 2} solution of PBu{sub 3} to give fcS{sub 2}CH{sub 2}. Molecular weights for [BufcS{sub 2}]n were confirmed by light scattering measurements. Soluble [BufcS{sub 2}]n undergoes reversible electrochemical oxidation in two steps, centered at 780 V (vs Ag/AgCl) and separated by {approximately}300 mV. The first oxidation potential is similar to that for the trisulfide monomer and is thought tomore » correspond to oxidation of alternating Fe centers, followed by conversion of the remaining Fe{sup II} sites. The polymers photodegrade upon exposure to UV light in air. Deselenization of BufcSe{sub 3} gave red soluble [BufcSe{sub 2}]n with only moderate molecular weights and with high polydispersities. The microstructure of this polymer was established by {sup 77}Se NMR studies which support the presence of head-to-head, head-to-tail, and tail-to-tail dyads. 21 refs., 9 figs., 2 tabs.« less