Synthetic and Electrochemical Studies on 1,1‘-Dithia-Substituted Derivatives of Ferrocene and Structure of 1,3-Dithia[3]ferrocenophane [Fe(C₅H₄S)₂CH₂]

Abstract

The bimetallic complexes fc(µ 2 -S) 2 TiCp 2 (1, fc ) 1,1′-ferrocenyl, Cp ) cyclopentadienyl) and fc(µ 2 -S 2 )(µ 2 -S)TiCp 2 (2) were synthesized by reaction of fc(SH) 2 with Cp 2 TiCl 2 , and from fcS 3 and Cp 2 Ti(CO) 2 , respectively. The novel tetrasulfane fcS 4 was obtained from 2 and SCl 2 . 1,3-Dithia[3]ferrocenophane fcS 2 CH 2 was obtained from fc(SH) 2 and CH 2 Cl 2 in the presence of Cp 2 TiCl 2 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-SO 2 , 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 Cp 2 Ti fragment exerts the opposite effect.

Ferrocene: An unrivaled electroactive building block for the design of push-pull dyes with near-infrared and infrared absorptions

“…This instability is notably the result of their facile reduction, notably for titanocenes. To improve their stability, an effective strategy consists in introducing heteroatoms such as oxygen, selenium or sulfur [168][169][170][171][172][173][174]. On this basis, a series of Zr and Ti-based metallocenes bearing ferrocene substitutes were examined for the spectroelectrochemical properties [175].…”

Trends in properties of para‐substituted 3‐(phenylhydrazo)pentane‐2,4‐diones

“…Correlations of the oxidation potential with Hammett's s p and related substituent constants have been reported in other systems, namely for series of coordination compounds bearing different substituents. [37,38,41,[64][65][66][67][68] In contrast, the reduction potential values do not vary appreciably with a change of the substituent, being rather close (À1.75 AE 0.07 V), what suggests an insignificant involvement of the substituent in the LUMO of HL [1][2][3][4][5] .…”

Synthesis and Electrochemical Behavior of Ferrocenyl‐Functionalized Metallocenes M(η5‐C5H5)2(EFc)2 (M = Ti, Zr; E = O, S, Se)

“…In contrast, less is known about ferrocenyl(alkyl)oxy, ferrocenylsulfanyl‐ and ferrocenylselanyl‐substituted metallocenes . For example, electrochemical studies on fc(µ 2 ‐ S 2 )(µ 2 ‐ S)[Ti] (fc = Fe(η 5 ‐ C 5 H 4 ) 2 , [Ti] = Ti(η 5 ‐ C 5 H 5 ) 2 ) were carried out displaying decomposition of this complex after initial ferrocene/ferrocenium oxidation resulting in a new unidentified species with a reversible process in the range for ferrocenyl groups …”