title: Impact of substituents and nonplanarity on nickel and copper porphyrin electrochemistry: first observation of a Cu(II)/Cu(III) reaction in nonaqueous media.
abstract: Electrochemical studies of the oxidation of dodecasubstituted and highly nonplanar nickel porphyrins in a noncoordinating solvent have previously revealed the first nickel(III) porphyrin dication. Herein, we investigate if these nonplanar porphyrins can also be used to detect the so far unobserved copper(III) porphyrin dication. Electrochemical studies of the oxidation of (DPP)Cu and (OETPP)Cu show three processes, the first two of which are macrocycle-centered to give the porphyrin dication followed by a Cu(II)/Cu(III) process at more positive potential. Support for the assignment of the Cu(II)/Cu(III) process comes from the linear relationships observed between E1/2 and the third ionization potential of the central metal ions for iron, cobalt, nickel, and copper complexes of (DPP)M and (OETPP)M. In addition, the oxidation behavior of additional nonplanar nickel porphyrins is investigated in a noncoordinating solvent, with nickel meso-tetraalkylporphyrins also being found to form nickel(III) porphyrin dications. Finally, examination of the nickel meso-tetraalkylporphyrins in a coordinating solvent (pyridine) reveals that the first oxidation becomes metal-centered under these conditions, as was previously noted for a range of nominally planar porphyrins.
authors.affiliation: Department of Chemistry, University of Houston , Houston, Texas 77204-5003, United States.
authors.forename: Yuanyuan
authors.initials: Y
authors.lastname: Fang
authors.forename: Mathias O
authors.initials: MO
authors.lastname: Senge
authors.forename: Eric
authors.initials: E
authors.lastname: Van Caemelbecke
authors.forename: Kevin M
authors.initials: KM
authors.lastname: Smith
authors.forename: Craig J
authors.initials: CJ
authors.lastname: Medforth
authors.forename: Min
authors.initials: M
authors.lastname: Zhang
authors.forename: Karl M
authors.initials: KM
authors.lastname: Kadish
mesh_terms: D003300:Copper / Q000737:chemistry*; D055664:Electrochemical Techniques; D008665:Metalloporphyrins / Q000138:chemical synthesis / Q000737:chemistry*; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry*
chemical_list: D008665:Metalloporphyrins; D011166:Porphyrins; D003300:Copper; D009532:Nickel