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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 ( L 2)] { L 2 = N(CHCHP t Bu 2 ) 2 - } is reported. The electrochemical characterization of [ReCl 2 ( L 2)] and comparison with our previously reported platform [ReCl 2 ( L 1)] { L 1 = N(CH 2 CH 2 P t Bu 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( L 2)] with electrophiles is presented., (© 2020 The Authors. Published by Wiley‐VCH Verlag GmbH & Co. KGaA.)