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Updated: Aug 20, 2025

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Stabilizing Doubly Deprotonated Diazomethane: Isolable Complexes with CN22- and CN2- Radical Ligands
Ze-Jie Lv1, Philipp D Engel2, Lukas Alig1
1Institut für Anorganische Chemie, University of Göttingen, Tammannstraße 4, 37077 Göttingen, Germany.
Abstract:
Transition metal complexes with a doubly deprotonated diazomethane (CNN2-) ligand have been proposed as fleeting intermediates in nitrogen transfer reactions. However, in contrast to isoelectronic azide (N3-), well-defined examples are unknown. We here report the synthesis and characterization of isolable complexes with terminal and bridging CNN2- 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 CO2 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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