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

ABSTRACT: Nitride complexes are key species in homogeneous nitrogen fixation to NH₃ via stepwise proton-coupled electron transfer (PCET). In contrast, direct generation of nitrogenous organic products from N₂ -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 N₂ 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 ne

SUBMITTER: Fritz M 

PROVIDER: S-EPMC9542086 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature