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Electrochemistry and spectral characterization of oxidized and reduced (TPPBr(x)())FeCl where TPPBr(x)() is the dianion of beta-brominated-pyrrole tetraphenylporphyrin and x varies from 0 to 8

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dc.contributor Wichita State University. Department of Chemistry en_US
dc.contributor.author Tagliatesta, Pietro en_US
dc.contributor.author Li, Jun en_US
dc.contributor.author Autret, Marie en_US
dc.contributor.author Van Caemelbecke, Eric en_US
dc.contributor.author Villard, Anne en_US
dc.contributor.author D'Souza, Francis en_US
dc.contributor.author Kadish, Karl M. en_US
dc.date.accessioned 2012-02-06T17:16:52Z
dc.date.available 2012-02-06T17:16:52Z
dc.date.issued 1996-09-11 en_US
dc.identifier 11666748.0 en_US
dc.identifier 0366543 en_US
dc.identifier ic960148c en_US
dc.identifier.citation Inorganic chemistry. 1996 Sep 11; 35(19): 5570-5576. en_US
dc.identifier.issn 1520-510X en_US
dc.identifier.issn 0020-1669 en_US
dc.identifier.uri http://hdl.handle.net/10057/4359
dc.description Full text of this article is not available in SOAR. en_US
dc.description.abstract The electrochemistry and spectroelectrochemistry of (TPPBr(x)())FeCl (TPPBr(x)() is the dianion of beta-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 pi ring system, and DeltaE(1/2) between these two electrode reactions increases as the molecule becomes more distorted. The overall reduction of each compound involves the stepwise electrogeneration omicronf an iron(II), iron(I), and iron(I) pi 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 (TPPBr(x)())FeCl (x = 0 to x = 6) forms both mono- and bis-CO adducts in CH(2)Cl(2). Only the mono-CO adduct is observed for (TPPBr(7))FeCl, and there is no binding at all of CO to (TPPBr(8))FeCl. The nu(CO) 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. en_US
dc.format.extent 5570-5576 en_US
dc.language.iso eng en_US
dc.publisher American Chemical Society en_US
dc.relation.ispartofseries Inorganic chemistry en_US
dc.relation.ispartofseries Inorg Chem en_US
dc.source NLM en_US
dc.title Electrochemistry and spectral characterization of oxidized and reduced (TPPBr(x)())FeCl where TPPBr(x)() is the dianion of beta-brominated-pyrrole tetraphenylporphyrin and x varies from 0 to 8 en_US
dc.type Article en_US
dc.description.version peer reviewed en_US
dc.rights.holder Copyright © 1996 American Chemical Society en_US

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