| Autor: |
Ushijima, Hirobumi, Akiyama, Takeo, Kajitani, Masatsugu, Shimizu, Kunio, Aoyama, Masahide, Masuda, Shigeru, Harada, Yoshiya, Sugimori, Akira |
| Zdroj: |
Bulletin of the Chemical Society of Japan; April 1990, Vol. 63 Issue: 4 p1015-1019, 5p |
| Abstrakt: |
1,2,3-Trithia[3]ferrocenophane (1a) and related compounds show a well-defined reversible one-electron oxidation wave (Fe(III)/Fe(II)) in cyclic voltammetry. The [3]ferrocenophanes with S and/or Se atoms in the bridge show unusually high oxidation half-wave potentials which have not been observed either in [3]ferrocenophane or in 1,1'-bis(methylchalcogeno)ferrocenes. The effect of chalcogen atoms at the 1,3-positions in the bridge on the positive shift of half-wave potentials is larger than that at the 2-position. Two kinds of electron-attracting effects of chalcogen atoms at the 1,3-positions in the bridge are proposed: an inductive electron-attracting effect (“through-bond” effect) and the interaction between the d-orbitals of Fe and chalcogen (“through-space” interaction). The role of the sulfur atom at the 2-position in the bridge is to stabilize the electron attracted by the sulfur atoms at the 1,3-positions by conjugation of three sulfur atoms. |
| Databáze: |
Supplemental Index |
| Externí odkaz: |
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