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http://dx.doi.org/10.18419/opus-14548
Autor(en): | Bens, Tobias Walter, Robert R. M. Beerhues, Julia Lücke, Clemens Gabler, Julia Sarkar, Biprajit |
Titel: | Isolation, characterization and reactivity of key intermediates relevant to reductive (electro)catalysis with Cp*Rh complexes containing pyridyl‐MIC (MIC=mesoionic carbene) ligands |
Erscheinungsdatum: | 2023 |
Dokumentart: | Zeitschriftenartikel |
Seiten: | 16 |
Erschienen in: | Chemistry - a European journal 30 (2024), No. e202302354 |
URI: | http://nbn-resolving.de/urn:nbn:de:bsz:93-opus-ds-145672 http://elib.uni-stuttgart.de/handle/11682/14567 http://dx.doi.org/10.18419/opus-14548 |
ISSN: | 1521-3765 0947-6539 |
Zusammenfassung: | In recent years, metal complexes of pyridyl‐mesoionic carbene (MIC) ligands have been reported as excellent homogeneous and molecular electrocatalysts. In combination with group 9 metals, such ligands form highly active catalysts for hydrogenation/transfer hydrogenation/hydrosilylation catalysis and electrocatalysts for dihydrogen production. Despite such progress, very little is known about the structural/electrochemical/spectroscopic properties of crucial intermediates for such catalytic reactions with these ligands: solvato complexes, reduced complexes and hydridic species. We present here a comprehensive study involving the isolation, crystallographic characterization, electrochemical/spectroelectrochemical/theoretical investigations, and in‐situ reactivity studies of all the aforementioned crucial intermediates involving Cp*Rh and pyridyl‐MIC ligands. A detailed mechanistic study of the precatalytic activation of [RhCp*] complexes with pyridyl‐MIC ligands is presented. Intriguingly, amphiphilicity of the [RhCp*]‐hydride complexes was observed, displaying the substrate dependent transfer of H+, H or H-. To the best of our knowledge, this study is the first of its kind targeting intermediates and reactive species involving metal complexes of pyridyl‐MIC ligands and investigating the interconversion amongst them. |
Enthalten in den Sammlungen: | 03 Fakultät Chemie |
Dateien zu dieser Ressource:
Datei | Beschreibung | Größe | Format | |
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CHEM_CHEM202302354.pdf | 3,82 MB | Adobe PDF | Öffnen/Anzeigen |
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