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• W1987795249 abstract "The electrochemistry and spectroelectrochemistry of (TPPBrx)FeCl (TPPBrx is the dianion of β-brominated-pyrrole tetraphenylporphyrin and x = 0−8) were examined in PhCN containing tetra-n-butylammonium perchlorate (TBAP) as supporting electrolyte. Each compound undergoes two reversible to quasireversible one-electron oxidations and either three or four reductions within the potential limits of the solvent. The two oxidations occur at the conjugated porphyrin π ring system, and ΔE1/2 between these two electrode reactions increases as the molecule becomes more distorted. The overall reduction of each compound involves the stepwise electrogeneration οf an iron(II), iron(I), and iron(I) π anion radical. An equilibrium between chloride-bound and chloride-free iron(II) forms of the porphyrin is observed with association of the anionic ligand being favored for compounds with x > 5. Singly reduced (TPPBrx)FeCl (x = 0 to x = 6) forms both mono- and bis-CO adducts in CH2Cl2. Only the mono-CO adduct is observed for (TPPBr7)FeCl, and there is no binding at all of CO to (TPPBr8)FeCl. The νCO of both the mono- and bis-adducts increases with increase in the number of Br groups, but in a nonlinear fashion which is explained in terms of two competing effects. One is the electron-withdrawing affinity of the Br substitutents and the other the nonplanarity of the macrocycle." @default.
• W1987795249 created "2016-06-24" @default.
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• W1987795249 date "1996-01-01" @default.
• W1987795249 modified "2023-10-03" @default.
• W1987795249 title "Electrochemistry and Spectral Characterization of Oxidized and Reduced (TPPBr<i>_x</i>)FeCl Where TPPBr<i>_x</i>Is the Dianion of β-Brominated-Pyrrole Tetraphenylporphyrin and<i>x</i>Varies from 0 to 8" @default.
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• W1987795249 doi "https://doi.org/10.1021/ic960148c" @default.
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• W1987795249 hasPublicationYear "1996" @default.
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