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Redox-Rich Metallocene Tetrazene Complexes: Synthesis, Structure, Electrochemistry, and Catalysis

Published version
Peer-reviewed

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Type

Article

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Authors

Vanicek, Stefan 
Jochriem, Markus 
Hassenrück, Christopher 

Abstract

Thermal or photochemical metal-centered cycloaddition reactions of azidocobaltocenium hexafluoridophosphate or azidoferrocene with (cyclooctadiene)(cyclopentadienyl)cobalt- (I) afforded the first metallocenyl-substituted tetrazene cyclopentadienyl cobalt complexes together with azocobaltocenium or azoferrocene as side products. The trimetallic CpCo compounds are highly conjugated, colored, and redox-active metallo-aromatic compounds, as shown by their spectroscopic, structural, and electrochemical properties. The CpCo-tetrazenido complex with two terminally appended cobaltocene units catalyzes electrochemical proton reduction from acetic acid at a mild overpotential (0.35 V). Replacing cobaltocene with ferrocene moieties rendered the complex inactive toward catalysis.

Description

Keywords

0306 Physical Chemistry (incl. Structural), 0302 Inorganic Chemistry, 0305 Organic Chemistry, 0303 Macromolecular and Materials Chemistry

Journal Title

Organometallics

Conference Name

Journal ISSN

1520-6041
1520-6041

Volume Title

Publisher

American Chemical Society (ACS)
Sponsorship
Christian Doppler Forschungsgesellschaft (unknown)
European Commission Horizon 2020 (H2020) Marie Sk?odowska-Curie actions (745604)
Austrian Science Fund (FWF), Christian Doppler Association (Austrian Federal Ministry for Digital and Economic Affairs, the National Foundation for Research, Technology and Development), OMV, Marie Skłodowska-Curie, Deutsche Forschungsgemeinschaft