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dc.contributor.authorMoore, William N. G.
dc.contributor.authorHenke, Wade C.
dc.contributor.authorLionetti, Davide
dc.contributor.authorDay, Victor W.
dc.contributor.authorBlakemore, James D.
dc.date.accessioned2020-11-30T15:50:54Z
dc.date.available2020-11-30T15:50:54Z
dc.date.issued2018-11-02
dc.identifier.citationMoore, W., Henke, W. C., Lionetti, D., Day, V. W., & Blakemore, J. D. (2018). Single-Electron Redox Chemistry on the [Cp*Rh] Platform Enabled by a Nitrated Bipyridyl Ligand. Molecules (Basel, Switzerland), 23(11), 2857. https://doi.org/10.3390/molecules23112857en_US
dc.identifier.urihttp://hdl.handle.net/1808/30936
dc.descriptionThis work is licensed under a Creative Commons Attribution 4.0 International License.en_US
dc.description.abstract[Cp*Rh] complexes (Cp* = pentamethylcyclopentadienyl) are attracting renewed interest in coordination chemistry and catalysis, but these useful compounds often undergo net two-electron redox cycling that precludes observation of individual one-electron reduction events. Here, we show that a [Cp*Rh] complex bearing the 4,4′-dinitro-2,2′-bipyridyl ligand (dnbpy) (3) can access a distinctive manifold of five oxidation states in organic electrolytes, contrasting with prior work that found no accessible reductions in aqueous electrolyte. These states are readily generated from a newly isolated and fully characterized rhodium(III) precursor complex 3, formulated as [Cp*Rh(dnbpy)Cl]PF6. Single-crystal X-ray diffraction (XRD) data, previously unavailable for the dnbpy ligand bound to the [Cp*Rh] platform, confirm the presence of both [η5-Cp*] and [κ2-dnbpy]. Four individual one-electron reductions of 3 are observed, contrasting sharply with the single two-electron reductions of other [Cp*Rh] complexes. Chemical preparation and the study of the singly reduced species with electronic absorption and electron paramagnetic resonance spectroscopies indicate that the first reduction is predominantly centered on the dnbpy ligand. Comparative cyclic voltammetry studies with [NBu4][PF6] and [NBu4][Cl] as supporting electrolytes indicate that the chloride ligand can be lost from 3 by ligand exchange upon reduction. Spectroelectrochemical studies with ultraviolet (UV)-visible detection reveal isosbestic behavior, confirming the clean interconversion of the reduced forms of 3 inferred from the voltammetry with [NBu4][PF6] as supporting electrolyte. Electrochemical reduction in the presence of triethylammonium results in an irreversible response, but does not give rise to catalytic H2 evolution, contrasting with the reactivity patterns observed in [Cp*Rh] complexes bearing bipyridyl ligands with less electron-withdrawing substituents.en_US
dc.description.sponsorshipUS National Science Foundation award OIA-1833087en_US
dc.description.sponsorshipKU Hall Chemical Research Funden_US
dc.description.sponsorshipCenter for Undergraduate Research at the University of Kansasen_US
dc.description.sponsorshipNIH S10OD016360en_US
dc.description.sponsorshipNIH S10RR024664en_US
dc.description.sponsorshipNSF MRI funding (CHE-1625923)en_US
dc.publisherMDPIen_US
dc.rights© 2018 by the authors. Licensee MDPI, Basel, Switzerland.en_US
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en_US
dc.subjectRhodiumen_US
dc.subjectElectrochemistryen_US
dc.subjectParamagneticen_US
dc.subjectSpectroelectrochemistryen_US
dc.subjectCatalysisen_US
dc.titleSingle-Electron Redox Chemistry on the [Cp*Rh] Platform Enabled by a Nitrated Bipyridyl Liganden_US
dc.typeArticleen_US
kusw.kuauthorMoore, William N. G.
kusw.kuauthorHenke, Wade C.
kusw.kuauthorLionetti, Davide
kusw.kuauthorDay, Victor W.
kusw.kuauthorBlakemore, James D.
kusw.kudepartmentChemistryen_US
dc.identifier.doi10.3390/molecules23112857en_US
dc.identifier.orcidhttps://orcid.org/0000-0001-5074-9341en_US
dc.identifier.orcidhttps://orcid.org/0000-0002-4574-8544en_US
dc.identifier.orcidhttps://orcid.org/0000-0002-4937-886Xen_US
dc.identifier.orcidhttps://orcid.org/0000-0003-4172-7460en_US
kusw.oaversionScholarly/refereed, publisher versionen_US
kusw.oapolicyThis item meets KU Open Access policy criteria.en_US
dc.identifier.pmidPMC6278249en_US
dc.rights.accessrightsopenAccessen_US


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© 2018 by the authors. Licensee MDPI, Basel, Switzerland.
Except where otherwise noted, this item's license is described as: © 2018 by the authors. Licensee MDPI, Basel, Switzerland.