title: Electron transfer activity of nickelacyclic complex analogues of nickelocene: synthesis of (eta(5)-R-cyclopentadienyl){eta(4)-[1-(eta(5)-R-cyclopentadienyl)]-2,3,4,5-tetraphenyl-1-nickela-2-cyclopentenyl}nickel complexes (R = H, CH(3)) and crystal structures of the redox couples [(eta(5)- methylcyclopentadienyl){eta(4)-[1-(eta(5)-methylcyclopentadienyl)]-2,3,4,5-tetraphenyl-1-nickela-2-cyclopentenyl}nickel]((0/+)) and [(eta(5)-methylcyclopentadienyl){eta(5)-[1-(eta(5)-methylcyclopentadienyl)-1-nickelafluorenyl}nickel]((0/+)).
abstract: Following previous reports on the synthesis and structure of different nickelacyclic complexes analogues of nickelocene, we now deal with the new metallacyclic compounds (eta5-R-cyclopentadienyl){eta4-[1-(eta5-R-cyclopentadienyl)]-2,3,4,5-tetraphenyl-1-nickela-2-cyclopentenyl}nickel (R = H, CH3). The redox ability of the whole series of nickelacyclic derivatives has been also investigated by electrochemical and spectroelectrochemical techniques, and the nature of the frontier orbitals responsible for the rich electron transfer activity of this class of compounds has been supported by theoretical considerations. On the basis of the redox properties of a few neutral members of the series, their chemical oxidation afforded the corresponding monocations and the crystal structures of the pertinent redox couples were determined by X-ray single-crystal analysis.
authors.affiliation: Dipartimento di Chimica, Università di Siena, Via De Gasperi 2, 53100 Siena, Italy.
authors.forename: Serena
authors.initials: S
authors.lastname: Losi
authors.forename: Fulvio
authors.initials: F
authors.lastname: Rossi
authors.forename: Franco
authors.initials: F
authors.lastname: Laschi
authors.forename: Fabrizia Fabrizi de
authors.initials: FF
authors.lastname: Biani
authors.forename: Piero
authors.initials: P
authors.lastname: Zanello
authors.forename: Piotr
authors.initials: P
authors.lastname: Buchalski
authors.forename: Kinga
authors.initials: K
authors.lastname: Burakowska
authors.forename: Katarzyna
authors.initials: K
authors.lastname: Piwowar
authors.forename: Jolanta
authors.initials: J
authors.lastname: Zbrzezna
authors.forename: Stanisaw
authors.initials: S
authors.lastname: Pasynkiewicz
authors.forename: Antoni
authors.initials: A
authors.lastname: Pietrzykowski
authors.forename: Kinga
authors.initials: K
authors.lastname: Suwińska
authors.forename: Lucjan
authors.initials: L
authors.lastname: Jerzykiewicz