Irradiation of rhodium(II) azido complex [Rh(N-3){N(CHCHPtBu2)(2)}] allowed for the spectroscopic characterization of the first reported rhodium complex with a terminal nitrido ligand. DFT computations reveal that the unpaired electron of rhodium(IV) nitride complex [Rh(N){N(CHCHPtBu2)(2)}] is located in an antibonding Rh-N pi* bond involving the nitrido moiety, thus resulting in predominant N-radical character, in turn providing a rationale for its transient nature and observed nitride coupling to dinitrogen.