title: Electrochemically driven intramolecular oxidative aromatic coupling as a pathway toward π-extended porphyrins.
abstract: A Ni(II) complex of a π-extended porphyrin bearing three mesityl substituents and one electron-rich naphthalene moiety has been prepared via electrochemical oxidation. It was proven that the whole oxidative process starts from electrochemical generation of a radical-cation on the porphyrin core. Electrochemistry and spectroelectrochemistry of both a naphthalenyl-substituted porphyrin and a porphyrin with a fused naphthalenyl group on the π-ring system provide clear distinction between metal- and ring-centered processes. The redox reactivity of the naphthalenyl-substituted metalloporphyrin in nonaqueous media is presented while outlining the most important structural factors which influence the reversible half-wave potentials for oxidation and reduction of this complex and the following chemical reactions which lead to an extended π-system.
authors.affiliation: Department of Chemistry, University of Houston, Texas 77204-5003, United States.
authors.forename: Ping
authors.initials: P
authors.lastname: Chen
authors.forename: Yuanyuan
authors.initials: Y
authors.lastname: Fang
authors.forename: Karl M
authors.initials: KM
authors.lastname: Kadish
authors.forename: Jan P
authors.initials: JP
authors.lastname: Lewtak
authors.forename: Dominik
authors.initials: D
authors.lastname: Koszelewski
authors.forename: Anita
authors.initials: A
authors.lastname: Janiga
authors.forename: Daniel T
authors.initials: DT
authors.lastname: Gryko
mesh_terms: D055664:Electrochemical Techniques; D008665:Metalloporphyrins / Q000737:chemistry*; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D010084:Oxidation-Reduction
chemical_list: D008665:Metalloporphyrins; D009532:Nickel