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Electron-Transfer Properties of Cp*FeP5: Evidence for Dimerization Reactions following both Oxidation and Reduction

Electron-Transfer Properties of Cp*FeP5: Evidence for Dimerization Reactions following both Oxidation and Reduction

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WINTER, Rainer, William GEIGER, 1999. Electron-Transfer Properties of Cp*FeP5: Evidence for Dimerization Reactions following both Oxidation and Reduction. In: Organometallics. 18(10), pp. 1827-1833. ISSN 0276-7333

@article{Winter1999Elect-13864, title={Electron-Transfer Properties of Cp*FeP5: Evidence for Dimerization Reactions following both Oxidation and Reduction}, year={1999}, doi={10.1021/om9809724}, number={10}, volume={18}, issn={0276-7333}, journal={Organometallics}, pages={1827--1833}, author={Winter, Rainer and Geiger, William} }

<rdf:RDF xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:dcterms="http://purl.org/dc/terms/" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/13864"> <dc:contributor>Geiger, William</dc:contributor> <dcterms:bibliographicCitation>First publ. in: Organometallics 18 (1999), 10, pp. 1827-1833</dcterms:bibliographicCitation> <dcterms:rights rdf:resource="http://nbn-resolving.org/urn:nbn:de:bsz:352-20140905103605204-4002607-1"/> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-06-29T05:37:39Z</dc:date> <dc:creator>Geiger, William</dc:creator> <dcterms:title>Electron-Transfer Properties of Cp*FeP5: Evidence for Dimerization Reactions following both Oxidation and Reduction</dcterms:title> <dc:contributor>Winter, Rainer</dc:contributor> <dc:language>eng</dc:language> <dcterms:issued>1999</dcterms:issued> <dcterms:abstract xml:lang="eng">The redox reactions of Cp*Fe(η5-P5) (1; Cp* = η5-C5Me5) have been characterized in nonaqueous solvents by electrochemical methods. As anticipated by analogy with ferrocene, 1 may be both oxidized and reduced in one-electron processes. Both processes are irreversible by cyclic voltammetry but reversible by bulk electrolysis. In CH2Cl2 complex 1 oxidizes initially to 17-electron 1+ (Ep,a = 0.57 V vs Fc), which rapidly equilibrates to give the dimeric dication [12]2+. An ESR spectrum attributed to 1+ is consistent with a d5 iron sandwich complex. A dimerization rate constant for 1+ of kD(17) = 1.4 × 104 M-1 s-1 was determined from cyclic voltammetry (CV) data. The dimeric dication quantitatively re-forms neutral 1 upon rereduction. Complex 1 undergoes reduction (E1/2 = −2.00 V) to 19-electron 1-, which also appears to dimerize in THF; kD(19) = ca. 6 × 105 M-1 s-1. Reoxidation of the diamagnetic dimer [12]2- regenerates 1. The shifts in potential induced when replacing a cyclopentadienyl ring by a pentaphosphacyclopentadienyl ring, explicable in terms of the weaker electron-donating ability of the latter, are greater for the reductions than the oxidations, implying an increased P5 character to the LUMO of 1 compared to the HOMO. Possible structures of the dimeric ions are discussed in terms of known structural analogues and previously published molecular orbital descriptions.</dcterms:abstract> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/13864"/> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-06-29T05:37:39Z</dcterms:available> <dc:creator>Winter, Rainer</dc:creator> <dc:rights>deposit-license</dc:rights> </rdf:Description> </rdf:RDF>

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