Synthesis, characterization and electrochemistry of diferrocenyl-1,3-thiazoles, 1,3-oxathiolanes, benzo-[b]-1,4-oxathiepines and ethyl 2-propenethioates

• Published in: Journal of organometallic chemistry 2020-09, Vol.922, p.121363, Article 121363
• Main Authors: Klimova, Elena I., Rubio, Carlos Guerrero, García-Valdés, Jesús, Nuñez-Cruz, Eder, Martínez-Klimova, Elena, Beletskaya, Irina P., Flores-Álamo, Marcos, Sánchez García, Jessica J.
• Format: Article
• Language: English
• Subjects: Ferrocenyloxathiepines; Ferrocenylpropenethioates; Ferrocenylvinyloxathiolanes; Ferrocenylvinylthiazoles
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2020.121363

2,3-Diferrocenylcyclopropenium salts react with bis-1,4-N,S- and bis-1,4-O,S-nucleophiles to yield: (1′,2′-diferrocenylvinyl)-1,3-thiazoles 6-8; (1′,2′-diferrocenylvinyl)-1,3-oxathiolanes 12a,b, 14a,b, 15b; 2,3-diferrocenyl-4H-1,4-benzo-[b]-oxathiepines 13a,b; ethyl2,3-diferrocenyl-2-propenethioates 16a,b and 2,3-diferrocenyl-3-methylthioacryl carbaldehydes Z/E-5b. New reactions for the synthesis of diferrocenyl heterocycles and diferrocenyl-2-propenethioates with several heteroatoms N,S, O and O,S, in molecules were found. The characterization of the new compounds was conducted by IR, 1H, 13C NMR spectroscopy, elemental analysis, and X-ray analysis of the compounds E-5b, 6 and 12b. The redox properties of the cycles 6, 8, 12a,b, 14a,b were investigated using cyclic (CV), differential pulse (DPV), and square wave (SWV) voltammetries. All compounds showed two reversible mono electronic oxidation processes since ΔEp(I) and ΔEp(II) are close to 0.060 V. Furthermore, the ΔE1/2 are enough separated to conclude that all the tested compounds have partially delocalized electronic charge in the mixed-valence state, according to the Robin-Day classification. Diferrocenylvinyl: thiazoles, -oxathiolanes, -oxathiepines and -2-propenethioates were obtained in the reactions of diferrocenylcyclopropenium cations with bis-1,4- N,S- and O,S-nucleophiles in the presence of Et3N. New methods for the synthesis of diferrocenyl-heterocycles and diferrocenyl-2-propenethioates with two or three heteroatoms N,S, N,O,S and O,S,S in molecules are found The characterization of the new compounds was conducted by IR, 1H and 13C NMR spectroscopy, elemental analysis, mass-spectrometry and X-ray diffraction. The redox properties of the diferrocenyl-heterocycles compounds were investigated using cyclic (CV), differential pulse (DPV), and square wave (SWV) voltammetries. [Display omitted] •New reactions of the diferrocenylcyclopropenium cations with bis-1,4-N,S- and bis-1,4-O,S-nucleophiles were studied.•The new method of synthesis of the diferrocenyl- (thiazoles, oxathiolanes, oxathiepines, propenethioates) is described.•Were determined the X-ray structures of diferrocenyl- (benzothiazole, benzooxathiolanes and methylthioacrylcarbaldehyde).•The diferrocenyl heterocycles showed two reversible mono electronic oxidation process since ΔEp(I) and ΔEp(II).