[ReCl3(PPh3)(2)(NCMe)] reacts with pincer ligand HN(CH2CH2PtBu2)(2) (HPNP) to five coordinate rhenium(III) complex [ReCl2(PNP)]. This compound cleaves N-2 upon reduction to give rhenium(V) nitride [Re(N)Cl(PNP)], as the first example in the coordination sphere of Re. Functionalization of the nitride ligand derived from N-2 is demonstrated by selective C N bond formation with MeOTf.