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dc.contributorWichita State University. Department of Chemistryen_US
dc.contributor.authorTagliatesta, Pietroen_US
dc.contributor.authorLi, Junen_US
dc.contributor.authorAutret, Marieen_US
dc.contributor.authorVan Caemelbecke, Ericen_US
dc.contributor.authorVillard, Anneen_US
dc.contributor.authorD'Souza, Francisen_US
dc.contributor.authorKadish, Karl M.en_US
dc.identifier.citationInorganic chemistry. 1996 Sep 11; 35(19): 5570-5576.en_US
dc.descriptionFull text of this article is not available in SOAR.en_US
dc.description.abstractThe 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.publisherAmerican Chemical Societyen_US
dc.relation.ispartofseriesInorganic chemistryen_US
dc.relation.ispartofseriesInorg Chemen_US
dc.titleElectrochemistry 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 8en_US
dc.description.versionpeer revieweden_US
dc.rights.holderCopyright © 1996 American Chemical Societyen_US

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