(Electro-)chemical Splitting of Dinitrogen with a Rhenium Pincer Complex

Abstract

The splitting of N2 into well‐defined terminal nitride complexes is a key reaction for nitrogen fixation at ambient conditions. In continuation of our previous work on rhenium pincer mediated N2 splitting, nitrogen activation and cleavage upon (electro)chemical reduction of [ReCl2(L2)] {L2 = N(CHCHPtBu2)2–} is reported. The electrochemical characterization of [ReCl2(L2)] and comparison with our previously reported platform [ReCl2(L1)] {L1 = N(CH2CH2PtBu2)2–} provides mechanistic insight to rationalize the dependence of nitride yield on the reductant. Furthermore, the reactivity of N2 derived nitride complex [Re(N)Cl(L2)] with electrophiles is presented. N2 splitting into terminal nitrides by chemical and electrochemical reduction of [ReCl2{N(CHCHPtBu2)2}] is presented. Comparison of electrochemical data with that of the previously reported, related pincer complex [ReCl2{N(CH2CH2PtBu2)2}] allowed for identifying key parameters that control the efficiency of the reaction sequence, which defines reductive N2 splitting. image John Wiley \u0026 Sons, Ltd.