Cationic Cycloheptatrienyl Cyclopentadienyl Manganese Sandwich Complexes : Tromancenium Explored with High-Power LED Photosynthesis

Lade...
Vorschaubild
Dateien
Basse_2-47k1grpkcmnv2.pdf
Basse_2-47k1grpkcmnv2.pdfGröße: 6.43 MBDownloads: 158
Datum
2021
Autor:innen
Basse, Reinhard
Vanicek, Stefan
Höfer, Thomas
Kopacka, Holger
Wurst, Klaus
Podewitz, Maren
Bildstein, Benno
et al.
Herausgeber:innen
Kontakt
ISSN der Zeitschrift
Electronic ISSN
ISBN
Bibliografische Daten
Verlag
Schriftenreihe
Auflagebezeichnung
ArXiv-ID
Internationale Patentnummer
Link zur Lizenz
Angaben zur Forschungsförderung
Projekt
Open Access-Veröffentlichung
Open Access Hybrid
Sammlungen
Core Facility der Universität Konstanz
Gesperrt bis
Titel in einer weiteren Sprache
Forschungsvorhaben
Organisationseinheiten
Zeitschriftenheft
Publikationstyp
Zeitschriftenartikel
Publikationsstatus
Published
Erschienen in
Zusammenfassung

In this contribution, we revisit the neglected and forgotten cationic, air-stable, 18-valence electron, heteroleptic sandwich complex (cycloheptatrienyl)(cyclopentadienyl)manganese, which was reported independently by Fischer and by Pauson about 50 years ago. Using advanced high-power LED photochemical synthesis, an expedient rapid access to the parent complex and to functionalized derivatives with alkyl, carboxymethyl, bromo, and amino substituents was developed. A thorough study of these "tromancenium" salts by a range of spectroscopic techniques (1H/13C/55Mn-NMR, IR, UV-vis, HRMS, XRD, XPS, EPR), cyclic voltammetry (CV), and quantum chemical calculations (DFT) shows that these manganese sandwich complexes are unique metallocenes with quite different chemical and physical properties in comparison to those of isoelectronic cobaltocenium salts or (cycloheptatrienyl)(cyclopentadienyl) sandwich complexes of the early transition metals. Electrochemically, all tromancenium ions undergo a chemically partially reversible oxidation and a chemically irreversible reduction at half-wave or peak potentials that respond to the substituents at the Cp deck. As exemplarily shown for the parent tromancenium ion, the product generated during the irreversible reduction process reverts at least partially to the starting material upon reoxidation. Quantum-chemical calculations of the parent tromancenium salt indicate that metal-ligand bonding is distinctly weaker for the cycloheptatrienyl ligand in comparison to that of the cyclopentadienyl ligand. Both the HOMO and the LUMO are metal and cycloheptatrienyl-ligand centered, indicating that chemical reactions will occur either metal-based or at the seven-membered ring, but not on the cyclopentadienyl ligand.

Zusammenfassung in einer weiteren Sprache
Fachgebiet (DDC)
540 Chemie
Schlagwörter
Konferenz
Rezension
undefined / . - undefined, undefined
Zitieren
ISO 690BASSE, Reinhard, Stefan VANICEK, Thomas HÖFER, Holger KOPACKA, Klaus WURST, Larissa A. CASPER, Moritz NAU, Rainer F. WINTER, Maren PODEWITZ, Benno BILDSTEIN, 2021. Cationic Cycloheptatrienyl Cyclopentadienyl Manganese Sandwich Complexes : Tromancenium Explored with High-Power LED Photosynthesis. In: Organometallics. American Chemical Society (ACS). 2021, 40(15), pp. 2736-2749. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/acs.organomet.1c00376
BibTex
@article{Basse2021-08-09Catio-54782,
  year={2021},
  doi={10.1021/acs.organomet.1c00376},
  title={Cationic Cycloheptatrienyl Cyclopentadienyl Manganese Sandwich Complexes : Tromancenium Explored with High-Power LED Photosynthesis},
  number={15},
  volume={40},
  issn={0276-7333},
  journal={Organometallics},
  pages={2736--2749},
  author={Basse, Reinhard and Vanicek, Stefan and Höfer, Thomas and Kopacka, Holger and Wurst, Klaus and Casper, Larissa A. and Nau, Moritz and Winter, Rainer F. and Podewitz, Maren and Bildstein, Benno}
}
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/123456789/54782">
    <dc:contributor>Wurst, Klaus</dc:contributor>
    <dc:contributor>Winter, Rainer F.</dc:contributor>
    <dc:language>eng</dc:language>
    <dc:contributor>Podewitz, Maren</dc:contributor>
    <dc:creator>Basse, Reinhard</dc:creator>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:contributor>Basse, Reinhard</dc:contributor>
    <dcterms:title>Cationic Cycloheptatrienyl Cyclopentadienyl Manganese Sandwich Complexes : Tromancenium Explored with High-Power LED Photosynthesis</dcterms:title>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2021-09-02T09:17:51Z</dc:date>
    <dc:creator>Nau, Moritz</dc:creator>
    <dcterms:abstract xml:lang="eng">In this contribution, we revisit the neglected and forgotten cationic, air-stable, 18-valence electron, heteroleptic sandwich complex (cycloheptatrienyl)(cyclopentadienyl)manganese, which was reported independently by Fischer and by Pauson about 50 years ago. Using advanced high-power LED photochemical synthesis, an expedient rapid access to the parent complex and to functionalized derivatives with alkyl, carboxymethyl, bromo, and amino substituents was developed. A thorough study of these "tromancenium" salts by a range of spectroscopic techniques (&lt;sup&gt;1&lt;/sup&gt;H/&lt;sup&gt;13&lt;/sup&gt;C/&lt;sup&gt;55&lt;/sup&gt;Mn-NMR, IR, UV-vis, HRMS, XRD, XPS, EPR), cyclic voltammetry (CV), and quantum chemical calculations (DFT) shows that these manganese sandwich complexes are unique metallocenes with quite different chemical and physical properties in comparison to those of isoelectronic cobaltocenium salts or (cycloheptatrienyl)(cyclopentadienyl) sandwich complexes of the early transition metals. Electrochemically, all tromancenium ions undergo a chemically partially reversible oxidation and a chemically irreversible reduction at half-wave or peak potentials that respond to the substituents at the Cp deck. As exemplarily shown for the parent tromancenium ion, the product generated during the irreversible reduction process reverts at least partially to the starting material upon reoxidation. Quantum-chemical calculations of the parent tromancenium salt indicate that metal-ligand bonding is distinctly weaker for the cycloheptatrienyl ligand in comparison to that of the cyclopentadienyl ligand. Both the HOMO and the LUMO are metal and cycloheptatrienyl-ligand centered, indicating that chemical reactions will occur either metal-based or at the seven-membered ring, but not on the cyclopentadienyl ligand.</dcterms:abstract>
    <dc:creator>Kopacka, Holger</dc:creator>
    <dc:creator>Casper, Larissa A.</dc:creator>
    <bibo:uri rdf:resource="https://kops.uni-konstanz.de/handle/123456789/54782"/>
    <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/54782/1/Basse_2-47k1grpkcmnv2.pdf"/>
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2021-09-02T09:17:51Z</dcterms:available>
    <dc:creator>Bildstein, Benno</dc:creator>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
    <dc:contributor>Vanicek, Stefan</dc:contributor>
    <dc:contributor>Kopacka, Holger</dc:contributor>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dcterms:issued>2021-08-09</dcterms:issued>
    <dc:contributor>Casper, Larissa A.</dc:contributor>
    <dc:contributor>Höfer, Thomas</dc:contributor>
    <dc:rights>Attribution 4.0 International</dc:rights>
    <dc:creator>Vanicek, Stefan</dc:creator>
    <dc:contributor>Bildstein, Benno</dc:contributor>
    <dc:creator>Winter, Rainer F.</dc:creator>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/54782/1/Basse_2-47k1grpkcmnv2.pdf"/>
    <dc:creator>Wurst, Klaus</dc:creator>
    <dc:creator>Höfer, Thomas</dc:creator>
    <dc:contributor>Nau, Moritz</dc:contributor>
    <dc:creator>Podewitz, Maren</dc:creator>
    <dcterms:rights rdf:resource="http://creativecommons.org/licenses/by/4.0/"/>
  </rdf:Description>
</rdf:RDF>
Interner Vermerk
xmlui.Submission.submit.DescribeStep.inputForms.label.kops_note_fromSubmitter
Kontakt
URL der Originalveröffentl.
Prüfdatum der URL
Prüfungsdatum der Dissertation
Finanzierungsart
Kommentar zur Publikation
Allianzlizenz
Corresponding Authors der Uni Konstanz vorhanden
Internationale Co-Autor:innen
Universitätsbibliographie
Ja
Begutachtet
Ja
Diese Publikation teilen