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

Vanicek, Stefan, Jochriem, Markus, Hassenrück, Christopher , Roy, Souvik, Kopacka, Holger, Wurst, Klaus, Müller, Thomas, Winter, Rainer F., Reisner, Erwin and Bildstein, Benno (2019) Redox-Rich Metallocene Tetrazene Complexes: Synthesis, Structure, Electrochemistry, and Catalysis. Organometallics, 38 (6). pp. 1361-1371. ISSN 0276-7333

Full content URL: https://doi.org/10.1021/acs.organomet.8b00681

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

Keywords:Organic acids, Redox reactions, Charge transfer, Ligands, Quantum mechanics
Subjects:F Physical Sciences > F100 Chemistry
F Physical Sciences > F161 Organometallic Chemistry
Divisions:College of Science > School of Chemistry
ID Code:40661
Deposited On:17 Apr 2020 12:41

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