Extremely Electron-Poor Bis(diarylmethylium)-Substituted Ferrocenes and the First Peroxoferrocenophane

Kurzanzeige
dc.contributor.authorCasper, Larissa A.
dc.contributor.authorOßwald, Steffen
dc.contributor.authorAnders, Patrick
dc.contributor.authorRosenbaum, Lisa-Catherine
dc.contributor.authorWinter, Rainer F.
dc.date.accessioned2020-03-10T12:00:48Z
dc.date.available2020-03-10T12:00:48Z
dc.date.issued2020-07-15
dc.description.abstractWe have prepared and studied extremely electron‐poor, deeply colored dicationic 1,1'‐bis(diarylmethylium)‐substituted ferrocenes [(η5‐C5H4‐CAr2)2Fe]2+ with various aryl substituents as their [B{C6H3(CF3)2‐3,5}4]– salts. Due to the strong acceptor substitution, the redox potential for the ferrocene‐based oxidation of the anisyl‐ or 2‐methylanisyl‐substituted congeners 1b2+ and 1c2+ is close to or even surpasses that of the second oxidation of parent ferrocene, i.e. the Cp2Fe+/2+ couple. The strongly Lewis‐acidic character of these complexes is manifest through strong interactions with donor solvents, which lead to a significant reduction of the intensities of the charge‐transfer bands in their electronic spectra and to solvatochromism. The reduced forms of the complexes tend to dimerize or oligomerize as revealed by EPR spectroscopy. Direduced 1b selectively reacts with molecular oxygen to form a peroxo‐bis(diarylmethyl)[4]ferrocenophane, which was also characterized by X‐ray crystallography.eng
dc.description.versionpublishedde
dc.identifier.doi10.1002/zaac.201900347eng
dc.identifier.ppn1727339991
dc.identifier.urihttps://kops.uni-konstanz.de/handle/123456789/48984
dc.language.isoengeng
dc.rightsAttribution 4.0 International
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/
dc.subject.ddc540eng
dc.titleExtremely Electron-Poor Bis(diarylmethylium)-Substituted Ferrocenes and the First Peroxoferrocenophaneeng
dc.typeJOURNAL_ARTICLEde
dspace.entity.typePublication
kops.citation.bibtex
@article{Casper2020-07-15Extre-48984,
  year={2020},
  doi={10.1002/zaac.201900347},
  title={Extremely Electron-Poor Bis(diarylmethylium)-Substituted Ferrocenes and the First Peroxoferrocenophane},
  number={13},
  volume={646},
  issn={0863-1786},
  journal={Zeitschrift für anorganische und allgemeine Chemie (ZAAC)},
  pages={712--725},
  author={Casper, Larissa A. and Oßwald, Steffen and Anders, Patrick and Rosenbaum, Lisa-Catherine and Winter, Rainer F.}
}
kops.citation.iso690CASPER, Larissa A., Steffen OSSWALD, Patrick ANDERS, Lisa-Catherine ROSENBAUM, Rainer F. WINTER, 2020. Extremely Electron-Poor Bis(diarylmethylium)-Substituted Ferrocenes and the First Peroxoferrocenophane. In: Zeitschrift für anorganische und allgemeine Chemie (ZAAC). Wiley. 2020, 646(13), pp. 712-725. ISSN 0863-1786. eISSN 1521-3749. Available under: doi: 10.1002/zaac.201900347deu
kops.citation.iso690CASPER, Larissa A., Steffen OSSWALD, Patrick ANDERS, Lisa-Catherine ROSENBAUM, Rainer F. WINTER, 2020. Extremely Electron-Poor Bis(diarylmethylium)-Substituted Ferrocenes and the First Peroxoferrocenophane. In: Zeitschrift für anorganische und allgemeine Chemie (ZAAC). Wiley. 2020, 646(13), pp. 712-725. ISSN 0863-1786. eISSN 1521-3749. Available under: doi: 10.1002/zaac.201900347eng
kops.citation.rdf
<rdf:RDF
    xmlns:dcterms="http://purl.org/dc/terms/"
    xmlns:dc="http://purl.org/dc/elements/1.1/"
    xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#"
    xmlns:bibo="http://purl.org/ontology/bibo/"
    xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#"
    xmlns:foaf="http://xmlns.com/foaf/0.1/"
    xmlns:void="http://rdfs.org/ns/void#"
    xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > 
  <rdf:Description rdf:about="https://kops.uni-konstanz.de/server/rdf/resource/123456789/48984">
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:contributor>Anders, Patrick</dc:contributor>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2020-03-10T12:00:48Z</dc:date>
    <dcterms:title>Extremely Electron-Poor Bis(diarylmethylium)-Substituted Ferrocenes and the First Peroxoferrocenophane</dcterms:title>
    <dc:creator>Winter, Rainer F.</dc:creator>
    <dc:creator>Oßwald, Steffen</dc:creator>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
    <dc:creator>Anders, Patrick</dc:creator>
    <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/48984/1/Casper_2-55a7w35jvgqr7.pdf"/>
    <dc:language>eng</dc:language>
    <dcterms:rights rdf:resource="http://creativecommons.org/licenses/by/4.0/"/>
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2020-03-10T12:00:48Z</dcterms:available>
    <dcterms:issued>2020-07-15</dcterms:issued>
    <dc:contributor>Rosenbaum, Lisa-Catherine</dc:contributor>
    <dc:creator>Rosenbaum, Lisa-Catherine</dc:creator>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dcterms:abstract xml:lang="eng">We have prepared and studied extremely electron‐poor, deeply colored dicationic 1,1'‐bis(diarylmethylium)‐substituted ferrocenes [(η&lt;sup&gt;5&lt;/sup&gt;‐C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;‐CAr&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Fe]&lt;sup&gt;2+&lt;/sup&gt; with various aryl substituents as their [B{C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;3&lt;/sub&gt;(CF&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;‐3,5}&lt;sub&gt;4&lt;/sub&gt;]– salts. Due to the strong acceptor substitution, the redox potential for the ferrocene‐based oxidation of the anisyl‐ or 2‐methylanisyl‐substituted congeners 1b&lt;sup&gt;2+&lt;/sup&gt; and 1c&lt;sup&gt;2+&lt;/sup&gt; is close to or even surpasses that of the second oxidation of parent ferrocene, i.e. the Cp&lt;sub&gt;2&lt;/sub&gt;Fe&lt;sup&gt;+/2+&lt;/sup&gt; couple. The strongly Lewis‐acidic character of these complexes is manifest through strong interactions with donor solvents, which lead to a significant reduction of the intensities of the charge‐transfer bands in their electronic spectra and to solvatochromism. The reduced forms of the complexes tend to dimerize or oligomerize as revealed by EPR spectroscopy. Direduced 1b selectively reacts with molecular oxygen to form a peroxo‐bis(diarylmethyl)[4]ferrocenophane, which was also characterized by X‐ray crystallography.</dcterms:abstract>
    <dc:creator>Casper, Larissa A.</dc:creator>
    <dc:contributor>Casper, Larissa A.</dc:contributor>
    <dc:contributor>Oßwald, Steffen</dc:contributor>
    <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/48984/1/Casper_2-55a7w35jvgqr7.pdf"/>
    <dc:contributor>Winter, Rainer F.</dc:contributor>
    <dc:rights>Attribution 4.0 International</dc:rights>
    <bibo:uri rdf:resource="https://kops.uni-konstanz.de/handle/123456789/48984"/>
  </rdf:Description>
</rdf:RDF>
kops.description.openAccessopenaccesshybrideng
kops.flag.isPeerReviewedtrueeng
kops.flag.knbibliographytrue
kops.identifier.nbnurn:nbn:de:bsz:352-2-55a7w35jvgqr7
kops.sourcefieldZeitschrift für anorganische und allgemeine Chemie (ZAAC). Wiley. 2020, <b>646</b>(13), pp. 712-725. ISSN 0863-1786. eISSN 1521-3749. Available under: doi: 10.1002/zaac.201900347deu
kops.sourcefield.plainZeitschrift für anorganische und allgemeine Chemie (ZAAC). Wiley. 2020, 646(13), pp. 712-725. ISSN 0863-1786. eISSN 1521-3749. Available under: doi: 10.1002/zaac.201900347deu
kops.sourcefield.plainZeitschrift für anorganische und allgemeine Chemie (ZAAC). Wiley. 2020, 646(13), pp. 712-725. ISSN 0863-1786. eISSN 1521-3749. Available under: doi: 10.1002/zaac.201900347eng
relation.isAuthorOfPublicationb82b38a3-4019-40cd-b72e-aa480692a5be
relation.isAuthorOfPublication94958998-aa28-4097-99c8-5bb70adfa363
relation.isAuthorOfPublication58dc3ab2-c4f5-4972-a1ca-31ff3c092c8e
relation.isAuthorOfPublication1a7b0319-f06d-4de1-9157-0a0da3c87a0c
relation.isAuthorOfPublication594af56c-6459-4c57-b7da-d30fb54e02e2
relation.isAuthorOfPublication.latestForDiscoveryb82b38a3-4019-40cd-b72e-aa480692a5be
source.bibliographicInfo.fromPage712
source.bibliographicInfo.issue13
source.bibliographicInfo.toPage725
source.bibliographicInfo.volume646
source.identifier.eissn1521-3749eng
source.identifier.issn0863-1786eng
source.periodicalTitleZeitschrift für anorganische und allgemeine Chemie (ZAAC)eng
source.publisherWileyeng

Dateien

Originalbündel

Gerade angezeigt 1 - 1 von 1
Vorschaubild nicht verfügbar
Name:
Casper_2-55a7w35jvgqr7.pdf
Größe:
3.64 MB
Format:
Adobe Portable Document Format
Beschreibung:
Casper_2-55a7w35jvgqr7.pdf
Casper_2-55a7w35jvgqr7.pdfGröße: 3.64 MBDownloads: 304

Sammlungen

Chemie: Publikationen