Naslov
Ferrocene-fused acenequinones: synthesis, structure and reaction chemistry

Autori
Mahrholdt, Julia ; Kovalski, Eduard ; Korb, Marcus ; Hildebrandt, Alexander ; Vrček, Valerije ; Lang, Heinrich

Izvornik
European journal of inorganic chemistry (1434-1948) 2021 (2021), 6; 578-589

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
ferrocene ; homoannular ; DFT ; (spectro)electrochemistry

Sažetak
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.

Izvorni jezik
Engleski

Znanstvena područja
Kemija, Farmacija

POVEZANOST RADA