Photochemical Dinitrogen Activation and Functionalization

by Katharina Oelschlegel
Doctoral thesis
Date of Examination:2025-12-04
Date of issue:2025-12-17
Advisor:Prof. Dr. Sven Schneider
Referee:Prof. Dr. Sven Schneider
Referee:Prof. Dr. Franc Meyer
Persistent Address: http://dx.doi.org/10.53846/goediss-11711

 

 

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Abstract

English

Photochemistry has emerged as a powerful tool for enabling challenging chemical transformations. In this thesis, light-driven strategies are explored for the conversion of dinitrogen into nitrogenous products beyond ammonia. A key step in N2 fixation is the homolytic cleavage of dinitrogen into terminal nitrides. Understanding the electronic structure of µ−N2 bridging complexes is essential for the development of catalysts. The study of the electronic structure of N2 bridging rheniumcomplexes is discussed by the use of a several spectroscopic methods. The combination of dinitrogen and dihydrogen with transition metal complexes remain rare. Identifying complexes capable of hydrogenating N2-derived molecules is therefore of crucial importance. By determining ground state and excited state properties of a novel photocatalyst in combination with Stern-Volmer analysis gives insight into the hydrogenation of the N2-derived ReV-imido complex. Further elucidation of the mechanism was done by transient absorption spectroscopy combined with TD-DFT. A new strategy for the conversion of dinitrogen into valuable organic nitrogen-containing chemicals is presented.
Keywords: N2 fixation; Photochemistry; PCET; Hydrogenation; PNP pincer; Porphyrine; Electronic Structure
 
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