Platinum-Mediated Dinitrogen Liberation from 2‑Picolyl Azide through a Putative PtN Double Bond Containing Intermediate

2-Picolyl azide reacts with cis-[PtCl2(DMSO)2] to form the diimino
complex [PtIICl2{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
N2 from the azide functionality. The prerequisites for
N2 liberation and for the stabilization of the nitrene-related
intermediate are analyzed in detail.