title: Thermically and electrochemically induced isomerization of a (bis(ferrocene)-cyclam)copper(II) complex.
abstract: The new bis(ferrocene)-cyclam macrocycle 1,8-bis(ferrocenylmethyl)-1,4,8,11-tetraazacyclotetradecane, denoted L, has been synthesized. Two Cu(II) complexes with L have been isolated and characterized from X-ray structure determination and electrochemical studies. These two LCu(II) complexes correspond to the type I (ferrocenyl subunits in the same side of the cyclam plane) and type III (ferrocenyl subunits above and below the cyclam plane) isomers. The type I LCu(II) complex was synthesized from L and a Cu(2+) salt, while the type III isomer was obtained by oxidation in air or by comproportionation of the Cu(I) complex. The interconversion between type I and type III LCu(II) complexes is negligible in acetonitrile and slow in dimethyl sulfoxide but fast via an electrochemical reduction-reoxidation cycle. According to UV-vis and electrochemical characterizations, the type III isomer is thermodynamically more stable and the type I isomer is kinetically favored. A type III LNi(II) complex was also isolated and characterized by X-ray diffraction analysis and from electrochemical studies.
authors.affiliation: Laboratoire d'Electrochimie Organique et de Photochimie Rédox, UMR CNRS 5630, Université Joseph Fourier Grenoble 1, BP 53, 38041 Grenoble Cédex 9, France.
authors.forename: Christophe
authors.initials: C
authors.lastname: Bucher
authors.forename: Jean-Claude
authors.initials: JC
authors.lastname: Moutet
authors.forename: Jacques
authors.initials: J
authors.lastname: Pécaut
authors.forename: Guy
authors.initials: G
authors.lastname: Royal
authors.forename: Eric
authors.initials: E
authors.lastname: Saint-Aman
authors.forename: Fabrice
authors.initials: F
authors.lastname: Thomas
authors.forename: Stéphane
authors.initials: S
authors.lastname: Torelli
authors.forename: Mihaela
authors.initials: M
authors.lastname: Ungureanu