Photoelectrochemical Conversion of Dinitrogen to Benzonitrile: Selectivity Control by Electrophile- versus Proton-Coupled Electron Transfer.

Nitride complexes are key species in homogeneous nitrogen fixation to NH via stepwise proton-coupled electron transfer (PCET). In contrast, direct generation of nitrogenous organic products from N -derived nitrides requires new strategies to enable efficient reductive nitride transfer in the presence of organic electrophiles. We here present a 2-step protocol for the conversion of dinitrogen to benzonitrile.

Cyanate Formation via Photolytic Splitting of Dinitrogen.

Light-driven N cleavage into molecular nitrides is an attractive strategy for synthetic nitrogen fixation. However, suitable platforms are rare. Furthermore, the development of catalytic protocols via this elementary step suffers from poor understanding of N-N photosplitting within dinitrogen complexes, as well as of the thermochemical and kinetic framework for coupled follow-up chemistry.