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

The splitting of N 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 splitting, nitrogen activation and cleavage upon (electro)chemical reduction of [ReCl(2)] {2 = N(CHCHPBu) } is reported. The electrochemical characterization of [ReCl(2)] and comparison with our previously reported platform [ReCl(1)] {1 = N(CHCHPBu) } provides mechanistic insight to rationalize the dependence of nitride yield on the reductant. Furthermore, the reactivity of N derived nitride complex [Re(N)Cl(2)] with electrophiles is presented.