Synthetic and electrochemical studies on 1,1 '-dithia-substituted derivatives of ferrocene and structure of 1,3-dithia[3]ferrocenophane [Fe(C5H4S)(2)CH2]

摘要

The bimetallic complexes fc(mu(2)-S)(2)TiCP2 (1,fc = 1,1'-ferrocenyl, Cp = cyclopentadienyl) and fc(mu(2)-S-2)(mu(2)-S)TiCp2 (2) were synthesized by reaction of fc(SH)(2) with Cp2TiC;(2), and from fcS(3) and CP2Ti(CO)(2), respectively. The novel tetrasulfane fcS(4) was obtained from 2 and SCl2. 1,3-Dithia[3]ferrocenophane fcS(2)CH(2) was obtained from fc(SH)(2) and CH2Cl2 in the presence of Cp2TiCl2 and KOH. The molecular and crystal structure of fcS(2)CH(2) was determined by X-ray crystallography; the molecular symmetry is C-s. Electrochemical studies on the recently prepared ferrocenophanes fcS(2)-1-SO, fcS(2)-1-SO2, and fcS(2)-2-SO show that, with respect to fcS(3), the progressive oxidation of the trisulfane bridge makes more and more difficult the fc/fc(+) oxidation, whereas insertion of a Cp2Ti fragment exerts the opposite effect. [References: 36]