title: Synthesis and redox behavior of ruthenocene-terminated oligoenes: characteristic and stable two-electron redox system and lower potential shift of the two-electron oxidation wave with elongating conjugation.
abstract: Ruthenocene-terminated butadienes and hexatrienes were prepared by the Wittig reaction of 3-ruthenocenyl-2-propenals with ruthenocenylmethylphosphonium salts and the Mukaiyama coupling of the propenals, respectively. Cyclic voltammetry of these complexes indicated that they were involved in a stable two-electron redox process. The oxidation potentials for ruthenocene-terminated oligoenes shifted progressively to lower potential with the increasing CH==CH units as follows: Rc--Rc (0.32 V)>RcCH==CHRc (+0.09 V)>Rc(CH==CH)(2)Rc (-0.06 V)>Rc(CH==CH)(3)Rc (-0.07 V), (Rc=ruthenocene). The tendency is in remarkable contrast to that in the successive one-electron redox process. These complexes were chemically oxidized to give stable crystalline solids, whose structures were confirmed by NMR spectroscopy and X-ray analysis to be oligoene analogues of a bis(fulvene) complex, for example, [(eta(5)-C(5)Me(5))Ru[mu(2)-eta(6):eta(6)-C(5)H(4)CH(CH==CH)(n)CHC(5)H(4)]Ru(eta(5)-C(5)Me(5))](2+) (n=1 or 2). The DFT calculation of the two-electron-oxidized species reproduced well the fulvene-complex structure for the ruthenocene moieties. Since both the neutral and oxidized species are stable and chemically reversible, this redox system may be serviceable as a two-electron version of the ferrocene one-electron redox system.
authors.affiliation: Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan. msato@chem.saitama-u.ac.jp
authors.forename: Masaru
authors.initials: M
authors.lastname: Sato
authors.forename: Toru
authors.initials: T
authors.lastname: Nagata
authors.forename: Atsushi
authors.initials: A
authors.lastname: Tanemura
authors.forename: Takashi
authors.initials: T
authors.lastname: Fujihara
authors.forename: Shigekazu
authors.initials: S
authors.lastname: Kumakura
authors.forename: Kei
authors.initials: K
authors.lastname: Unoura