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