Synthesis, structure, and fungicidal activity of thia- and aza-ferrocenophanes

Abstract

Reaction of bridging dicyclopentadienyl disodium E(CH₂COCpNa)₂ (E = S or NPh, Cp = cyclopentadienyl) with FeCl₂ yields thia- and aza-[5]ferrocenophanes E(CH₂COCp)₂Fe [E = S (1) and NPh (2)]. Treatment of C₁₄H₈(CH₂SCH₂COCpNa)₂ (C₁₄H₈ = 9,10-anthracenyl) with FeCl₂ affords dithia-[12]ferrocenophane C₁₄H₈(CH₂SCH₂COCp)₂Fe (3), while similar reaction of C₆H₄(CH₂SCH₂COCpNa)₂ (C₆H₄ = 1,4-phenyl) with FeCl₂ provides a mixture of dithia-[12]ferrocenophane C₆H₄(CH₂SCH₂COCp)₂Fe (4) and tetrathia-[12,12]ferrocenophane [C₆H₄(CH₂SCH₂COCp)₂Fe]₂ (5), which are separated easily by column chromatography. These five compounds were characterized by IR and NMR spectroscopic analyses and the structures of 2 and 3 were further confirmed by single crystal X-ray diffraction. The electrochemical behaviors of 1–4 were investigated by cyclic voltammetry. In addition, their fungicidal activities against Alternaria solani, Cercospora arachidicola, Physalospora piricola, and Botrytis cinerea were tested in vitro.

Keywords:

• Ferrocenophane
• Electrochemical property
• Fungicidal activity
• Bioorganometallic chemistry

Acknowledgment

This work is supported by the National Natural Science Foundation of China (no. 20721062).