Publikation:

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: 208

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
Core Facility der Universität Konstanz

Gesperrt bis

Titel in einer weiteren Sprache

Publikationstyp
Zeitschriftenartikel
Publikationsstatus
Published

Erschienen 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

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

Forschungsvorhaben

Organisationseinheiten

Zeitschriftenheft

Zugehörige Datensätze in KOPS

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