Ferrocene-Fused Acenequinones: Synthesis, Structure and Reaction Chemistry

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • J. Mahrholdt - (Author)
  • E. Kovalski - (Author)
  • Marcus Korb - (Author)
  • A. Hildebrandt - , Chemnitz University of Technology (Author)
  • V. Vrček - (Author)
  • Heinrich Lang - (Author)

Abstract

The synthesis of anti-[1.1](2,17)(6,13)ferrocenophane-1,12-dione (2) is discussed. By addition of LiAlH4, NaBH4 or Wittig's reagent only one keto group reacted to give HO- or cC3H4-functionalized [1.1](2,17)(6,13)ferrocenophan-12-hydroxy-1-one (3) and [1.1](2,17)(6,13)ferrocenophan-12-cyclopropane-1-one (4). Exchange of CO by CS groups is possible upon addition of Lawesson's reagent to 2 forming [1.1](2,17)(6,13)ferrocenophan-1,12-dithioketone (5). Theoretical studies confirm the different reactivities of the CO groups. Electrochemical studies on 2–5 showed separated reversible one-electron events for 2–4 (125–925 mV) and an irreversible one for 5. The ferrocenyls in 4 are easier to oxidize, due to their higher electron-richness. In 2 a larger redox separation comes about suggesting a stronger intermetallic interaction between FeII/FeIII in the mixed-valent species. In situ UV-vis/NIR studies confirm that 2 is a weak coupled class II system according to the classification of Robin and Day. Compounds 3 and 4 display electrostatic interactions among the ferrocenyls as oxidation progresses.

Details

Original languageEnglish
Pages (from-to)578-589
Number of pages12
JournalEuropean journal of inorganic chemistry
Volume2021
Issue number6
Publication statusPublished - 12 Feb 2021
Peer-reviewedYes
Externally publishedYes

External IDs

Scopus 85097365442
Mendeley e36f7112-7435-34b7-9121-4a17f7ebf5fb

Keywords

ASJC Scopus subject areas

Keywords

  • (Spectro)Electrochemistry, DFT, Diketone, Ferrocene, Homoannular, Reaction chemistry, Solid state structure