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(3) via stepwise proton‐coupled electron transfer (PCET). In contrast, direct generation of nitrogenous organic products from N(2)‐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. Photoelectrochemical, reductive N(2) splitting produces a rhenium(V) nitride with unfavorable PCET thermochemistry towards ammonia generation. However, N‐benzoylation stabilizes subsequent reduction as a basis for selective nitrogen transfer in the presence of the organic electrophile and Brønsted acid at mild reduction potentials. This work offers a new strategy for photoelectrosynthetic nitrogen fixation beyond ammonia—to yield nitrogenous organic products.