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

The splitting of N(2) 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 N(2) splitting, nitrogen activation and cleavage upon (electro)chemical reduction of [ReCl(2)(L2)] {L2 = N(CHCHPtBu(2))(2) (–)} is reported. The electrochemical characterization of [ReCl(2)(L2)] and comparison with our previously reported platform [ReCl(2)(L1)] {L1 = N(CH(2)CH(2)PtBu(2))(2) (–)} provides mechanistic insight to rationalize the dependence of nitride yield on the reductant. Furthermore, the reactivity of N(2) derived nitride complex [Re(N)Cl(L2)] with electrophiles is presented.