Electrochemical N2-splitting and functionalisation in the coordination sphere of Rhenium

by Richt Sieteke van Alten
Doctoral thesis
Date of Examination:2021-06-21
Date of issue:2021-07-13
Advisor:Prof. Dr. Sven Schneider
Referee:Prof. Dr. Sven Schneider
Referee:Prof. Dr. Inke Siewert
Persistent Address: http://dx.doi.org/10.53846/goediss-8727

 

 

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Abstract

English

This thesis describes the exchange of stoichiometric, wasteful chemical redox-reagents with electrochemical activation methods within a rhenium-mediated N2-splitting and functionalisation cycle. After establishing electrochemical N2 splitting into a molecular defined nitride complex, a mechanistic pathway was proposed for this reaction based on extensive spectroscopic and electrochemical studies. Subsequently, two series of different rhenium complexes with modified ancillary ligands were synthesised to substantiate and expand our mechanistic understanding and to formulate design parameters for the development of future electrocatalysts. Furthermore, the oxidative functionalization of the nitrides towards acetonitrile was transformed towards electrochemical activation and extended to an additional platform. Hereby, a stoichiometric N2 splitting and functionalization cycle was electrified.
Keywords: Electrochemistry; Organometallic chemistry; N2 splitting and functionalisation; Rhenium; Spectroscopy; Electrolysis; structure-reactivity relationsships
 
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