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Synthesis and electrochemical behavior of ferrocenyl β-ketoamines FcC(O)CH=C(NH(C6H4-4-R‘)R

FcC(O)CH=C(OH)R (1, R = Me ; 2, R = Fc ; Fc = Fe(η5-C5H4)(η5-C5H5)) reacts with 1-H2N-4-R’-C6H4 (3a, R‘ = Me ; 3b, R‘ = OMe ; 3c, R‘ = C≡N ; 3d, R‘ = F) producing β-ketoamines FcC(O)CH=C(NH(C6H4- 4-R‘)R (4a–d, R = Me ; 5a-d, R =Fc). Electrochemistry shows that 4a–d possess one (4a: E°′ = 90 mV ; 4b: E°′ = 80 mV ; 4c: E°′ = 145 mV ; 4d: E°′ = 95 mV) and 5a–d two (5a: E°′1, 2 = 90, 305 mV ; 5b: E°′1, = 85, 305 mV ; 5c: E°′1, 2 = 155, 360 mV ; 5d: E°′1, 2 = 105, 325 mV) reversible redox processes. In 5a–d electrostatic interactions occur among Fc/[Fc]+ as oxidation progresses, as evidenced by UV/vis-NIR spectroscopy. Compounds 4a, d and 5b, cdisplay an irreversible N-oxidation at 1100 – 1450 mV, while 4b owns a reversible event at 910 mV. A linear relationship between the σ Hammett constants and the E°′1values exists.

electrochemistry ; ferrocenyl β-ketoamines ; solid-state structure ; spectroelectrochemistry

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