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Electronic interactions in oligoferrocenes with cationic, neutral and anionic four-coordinate boron bridges

Electronic interactions in oligoferrocenes with cationic, neutral and anionic four-coordinate boron bridges

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SCHEIBITZ, Matthias, Julia HEILMANN, Rainer WINTER, Michael BOLTE, Jan BATS, Matthias WAGNER, 2005. Electronic interactions in oligoferrocenes with cationic, neutral and anionic four-coordinate boron bridges. In: Dalton Transactions(1), pp. 159-170. ISSN 1477-9226

@article{Scheibitz2005-01-07Elect-13807, title={Electronic interactions in oligoferrocenes with cationic, neutral and anionic four-coordinate boron bridges}, year={2005}, doi={10.1039/b413581d}, number={1}, issn={1477-9226}, journal={Dalton Transactions}, pages={159--170}, author={Scheibitz, Matthias and Heilmann, Julia and Winter, Rainer and Bolte, Michael and Bats, Jan and Wagner, Matthias} }

<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/123456789/13807"> <dcterms:rights rdf:resource="http://nbn-resolving.org/urn:nbn:de:bsz:352-20140905103605204-4002607-1"/> <dc:contributor>Bolte, Michael</dc:contributor> <dc:contributor>Scheibitz, Matthias</dc:contributor> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-06-22T09:20:47Z</dc:date> <dc:creator>Winter, Rainer</dc:creator> <dc:rights>deposit-license</dc:rights> <dc:language>eng</dc:language> <dc:contributor>Heilmann, Julia</dc:contributor> <dc:creator>Bats, Jan</dc:creator> <dc:contributor>Winter, Rainer</dc:contributor> <dc:creator>Bolte, Michael</dc:creator> <dc:creator>Wagner, Matthias</dc:creator> <dc:contributor>Bats, Jan</dc:contributor> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/13807"/> <dcterms:bibliographicCitation>First publ. in: Dalton Transactions 2005, 1, pp. 159-170</dcterms:bibliographicCitation> <dc:creator>Scheibitz, Matthias</dc:creator> <dcterms:title>Electronic interactions in oligoferrocenes with cationic, neutral and anionic four-coordinate boron bridges</dcterms:title> <dcterms:issued>2005-01-07</dcterms:issued> <dc:contributor>Wagner, Matthias</dc:contributor> <dcterms:abstract xml:lang="eng">Dinuclear and trinuclear ferrocene complexes {[Fc2BMe2]Li, [Fc-BMe2-fc-BMe2-Fc]Li2, Fc2B(pyind), [Fc2B(bipy)]PF6, [Fc-B(bipy)-fc-B(bipy)-Fc](PF6)2} bearing anionic, uncharged, and cationic four-coordinate boron bridges have been synthesized (Fc: ferrocenyl; fc: 1,1′-ferrocenylene; pyind: 5-fluoro-2-(2′-pyridyl)indolyl; bipy: 2,2′-bipyridyl). The molecular structures of [Fc2BMe2]Li(12-crown-4)2, [Fc-BMe2-fc-BMe2-Fc](Li(12-crown-4)2)2, Fc2B(pyind), and [Fc2B(bipy)]PF6 were determined by X-ray crystallography. The anionic aggregates [Fc2BMe2]− and [Fc-BMe2-fc-BMe2-Fc]2− are very sensitive to air and moisture whereas bromide salts of their cationic counterparts [Fc2B(bipy)]+ and [Fc-B(bipy)-fc-B(bipy)-Fc]2+ may be dissolved in water without decomposition. Cyclic voltammograms of the diferrocene species show two well-resolved one-electron transitions separated by 0.21 V ([Fc2BMe2]Li; E°′ = −0.43 V, −0.64 V; vs. FcH/FcH+), 0.18 V (Fc2B(pyind); E°′ = −0.03 V, −0.21 V), and 0.16 V ([Fc2B(bipy)]PF6; E°′ = +0.23 V, +0.07 V), which indicates electronic interactions between the two ferrocenyl substituents. Two redox waves with an intensity ratio of 1 ∶ 2 are observed in the cyclic voltammograms of the trinuclear derivatives [Fc-BMe2-fc-BMe2-Fc]Li2 and [Fc-B(bipy)-fc-B(bipy)-Fc](PF6)2. In the case of the BMe2-bridged species, the electrochemically unique central ferrocenylene unit is oxidized at a much more cathodic potential value (E°′ = −1.21 V) than the two terminal ferrocenyl substituents (E°′ = −0.51 V). The opposite is true in the case of the B(bipy)-bridged trimer where oxidation of the terminal ferrocenyl groups (E°′ = +0.03 V) precedes oxidation of the internal iron atom (E°′ = +0.26 V). The Fe(II)/Fe(III) redox potentials of the mono- and dianionic species differ to a much larger extent from the redox potential of parent ferrocene (E°′ = 0 V) than the E°′ values of the corresponding mono- and dicationic derivatives. Apart from electrostatic interactions, the electrochemical properties of BMe2- and B(bipy)-bridged oligoferrocenes are determined by the pronounced positive inductive effect of triorganoborate substituents together with positive σ/π* hyperconjugation on the one hand and ferrocene-to-B(bipy) charge transfer on the other.</dcterms:abstract> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-06-22T09:20:47Z</dcterms:available> <dc:creator>Heilmann, Julia</dc:creator> </rdf:Description> </rdf:RDF>

Dateiabrufe seit 01.10.2014 (Informationen über die Zugriffsstatistik)

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