2-Picolyl azide reacts with cis-[PtCl2(DMSO)(2)] to form the diimino complex [(PtCl2)-Cl-II{NH=C(H)Py}] with subsequent dinitrogen liberation. The formation of the latter complex is scrutinized in a combined experimental and theoretical analysis. We establish in silico that the transformation involves a highly reactive intermediate containing a Pt=N double bond formed after the extrusion of N-2 from the azide functionality. The prerequisites for N-2 liberation and for the stabilization of the nitrene-related intermediate are analyzed in detail.