title: 5,10,15-Triferrocenylcorrole Complexes.
abstract: Complexes of 5,10,15-triferrocenylcorrole were synthesized from the crude free-base corrole product obtained by the reaction of ferrocenyl aldehyde and pyrrole. Direct formation of the complex in this manner leads to an increase of the reaction yield by protecting the corrole ring toward oxidative decomposition. The procedure was successful and gave the expected product in the case of the copper and triphenylphosphinecobalt complexes, but an unexpected result was obtained in the case of the nickel derivative, where metal insertion led to a ring opening of the macrocycle at the 5 position, giving as a final product a linear tetrapyrrole nickel complex bearing two ferrocenyl groups. The purified 5,10,15-triferrocenylcorrole complexes have been fully characterized by a combination of spectroscopic methods, electrochemistry, spectroelectrochemistry, and density functional theory calculations. Copper derivatives of 10-monoferrocenyl- and 5,15-diferrocenylcorrole were prepared to investigate how the number and position of the ferrocenyl groups influenced the spectroscopic and electrochemical properties of the resulting complexes. A complete assignment of resonances in the (1)H and (13)C NMR spectra was performed for the cobalt and nickel complexes, and detailed electrochemical characterization was carried out to provide additional insight into the degree of communication between the meso-ferrocenyl groups on the conjugated macrocycle and the central metal ion of the ferrocenylcorrole derivatives.
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.affiliation: Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata , via della Ricerca Scientifica 1, 00133 Rome, Italy.
authors.forename: Pierluca
authors.initials: P
authors.lastname: Galloni
authors.affiliation: Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata , via della Ricerca Scientifica 1, 00133 Rome, Italy.
authors.forename: Federica
authors.initials: F
authors.lastname: Mandoj
authors.affiliation: Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata , via della Ricerca Scientifica 1, 00133 Rome, Italy.
authors.forename: Sara
authors.initials: S
authors.lastname: Nardis
authors.affiliation: Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata , via della Ricerca Scientifica 1, 00133 Rome, Italy.
authors.forename: Manuela
authors.initials: M
authors.lastname: Stefanelli
authors.affiliation: Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata , via della Ricerca Scientifica 1, 00133 Rome, Italy.
authors.forename: Andrea
authors.initials: A
authors.lastname: Vecchi
authors.affiliation: Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata , via della Ricerca Scientifica 1, 00133 Rome, Italy.
authors.forename: Sara
authors.initials: S
authors.lastname: Lentini
authors.affiliation: Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata , via della Ricerca Scientifica 1, 00133 Rome, Italy.
authors.forename: Daniel O
authors.initials: DO
authors.lastname: Cicero
authors.affiliation: Department of Chemistry, University of Houston , Houston, Texas 77204-5003, United States.
authors.forename: Yan
authors.initials: Y
authors.lastname: Cui
authors.affiliation: Department of Chemistry, University of Houston , Houston, Texas 77204-5003, United States.
authors.forename: Lihan
authors.initials: L
authors.lastname: Zeng
authors.affiliation: Department of Chemistry, University of Houston , Houston, Texas 77204-5003, United States.
authors.forename: Karl M
authors.initials: KM
authors.lastname: Kadish
authors.affiliation: Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata , via della Ricerca Scientifica 1, 00133 Rome, Italy.
authors.forename: Roberto
authors.initials: R
authors.lastname: Paolesse
mesh_terms: D066241:Carbon-13 Magnetic Resonance Spectroscopy; D004563:Electrochemistry; D058085:Iron Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D011166:Porphyrins / Q000737:chemistry*; D066244:Proton Magnetic Resonance Spectroscopy; D013056:Spectrophotometry, Ultraviolet
chemical_list: D058085:Iron Compounds; D011166:Porphyrins; C431863:corrole