Transition metal complexes with a doubly deprotonated diazomethane (CNN) ligand have been proposed as fleeting intermediates in nitrogen transfer reactions. However, in contrast to isoelectronic azide (N), well-defined examples are unknown. We here report the synthesis and characterization of isolable complexes with terminal and bridging CNN ligands, stabilized by platinum(II) pincer fragments. Bonding within the allenic dimetallanitrilimine core (Pt-N═N═C-Pt) was probed by oxidation of the bridging ligand. Enhanced reactivity toward [3 + 2]-cycloaddition with CO was obtained. Photofragmentation favors N-NC over NN-C bond cleavage as a route to cyanide and a transient metallonitrene complex.
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