Electrochemical Acetonitrile Release from Dinitrogen-Derived Rhenium Imido Complexes through Proton-Coupled Electron Transfer
Year: 2026
Type: article
Abstract: The oxidation of rhenium(III) azavinylidene complexes that originate from the reductive splitting of dinitrogen enables the stepwise conversion of N2 to nitriles. We here report the development of an electrochemical protocol and the experimental and computational examination of the reaction mechanism. Electrolysis of N2-derived {ReIII–N═CHCH3} azavinylidene complexes in the presence of chloride and NEt3 affords MeCN nearly quantitatively and the respective ReIV 3-electron oxidation products in yields around 50%. The lower yields in the Re product can be attributed to degradation processes of the supporting pincer ligands. The first oxidation is coupled to chloride addition. Subsequent proton-coupled electron transfer (PCET) affords the nitrile product as a net 2-electron oxidation of the nitrogenous ligand. The overoxidation to rhenium(IV) originates in a large potential inversion upon restoration of rhenium(III) as an inherent feature to the mechanism.
Source: Inorganic Chemistry
Institution: University of Göttingen
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W7225729474