Abstract
The reactions of 1,1′-bis(hydroxymethyl)ferrocene with amines primary atnines such as 6-aminohexanol, cyclohexylamine, 4-phenylbutylamine, 2-isopropylaniline, 4-(trifluoromethyl)benzylamine, and 1-aminomethylferrocene in the presence of [RuCl 2 (PPh 3 ) 3 ] catalyst led to intermolecular condensation of the CH 2 OH and NH 2 groups to afford N-alkyl- or N-aryl substituted 2-aza-[3]-(1,1′)-ferrocenophanes. Cyclic voltammograms of the obtained N-alkyl-2-aza-[3]-(1,1′)-ferrocenophanes exhibit reversible redox of the Fe center at E 1/2 = -0.01 - +0.04 V (vs Ag + /Ag) and subsequent irreversible oxidation of the amino group of the ligand at E ox = 0.41-0.44 V. N-(4-Hydroxyphenyl)-2-aza-[3]-(1,1′)-ferrocenophane shows two pairs of reversible electrochemical oxidation and reduction at E 1/2 = 0.04 and 0.44 V. The latter potential is significantly lower than the corresponding electrochemical oxidation of N-aryl-2-aza-[3]-(1,1′)-ferrocenophanes (0.68-0.75 V). The N-alkyl-2-aza-[3]-(1,1′)-ferrocenophanes react with MeI to cause methylation of the amino group to produce cationic 2-aza-[3]-(1,1′)-ferrocenophanes containing a quaternary nitrogen center. The iodo counter anion is easily replaced with BF4 - or PF6 - . Cyclic voltammograms of the cationic ferrocenophanes show the redox between ferrocene and ferrocenium at E 1/2 = 0.37-0.42 V.