title: Synthesis and characterization of free-base, copper, and nickel isocorroles.
abstract: A series of free-base and metalated isocorroles represented as (TT-n-iso-Cor)H(2) and (TT-n-iso-Cor)M(II), where n = 5 or 10 and M = Ni or Cu, were synthesized and characterized by electrochemistry and spectroelectrochemistry in CH(2)Cl(2) containing 0.1 M tetra-n-butylammonium perchlorate. The metalation of the free-base macrocycles with Co(II), Mn(III), or Zn(II) was also attempted but was unsuccessful. Six isocorroles were isolated and shown to undergo two stepwise oxidations to give pi-cation radicals and dications in CH(2)Cl(2), with the most stable products being obtained in the case of the 10-substituted derivatives. The same isocorroles could also be reduced by one or two electrons, but the initial one-electron addition products are unstable and undergo a rapid chemical reaction giving a reduced corrole or corrole-like product, which could be reoxidized to the corresponding (TTCor)M at a controlled positive potential. This series of reactions effectively illustrates an isocorrole to corrole conversion upon reduction and reoxidation and was monitored by both electrochemistry and thin-layer spectroelectrochemistry.
authors.affiliation: Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata, via della Ricerca Scientifica, 1, 00133 Rome, Italy.
authors.forename: Giuseppe
authors.initials: G
authors.lastname: Pomarico
authors.forename: Xiao
authors.initials: X
authors.lastname: Xiao
authors.forename: Sara
authors.initials: S
authors.lastname: Nardis
authors.forename: Roberto
authors.initials: R
authors.lastname: Paolesse
authors.forename: Frank R
authors.initials: FR
authors.lastname: Fronczek
authors.forename: Kevin M
authors.initials: KM
authors.lastname: Smith
authors.forename: Yuanyuan
authors.initials: Y
authors.lastname: Fang
authors.forename: Zhongping
authors.initials: Z
authors.lastname: Ou
authors.forename: Karl M
authors.initials: KM
authors.lastname: Kadish
mesh_terms: D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004563:Electrochemistry; D008665:Metalloporphyrins / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D008665:Metalloporphyrins; D009942:Organometallic Compounds; D003300:Copper; D009532:Nickel