Design,Synthesis, and Structural Analysis of Divalent NI Compounds and Identification of a New Electron‐Donating Ligand

The dative‐bond representation (L→E) in compounds with main group elements (E) has triggered extensive debate in the recent past. The scope and limits of this nonclassical coordination bond warrant comprehensive exploration. Particularly compounds with (L→N←L′)⁺ arrangement are of special interest because of their therapeutic importance. This work reports the design and synthesis of novel chemical species with the general structural formula (L→N←L′)⁺ carrying the unusual ligand cyclohexa‐2,5‐diene‐4‐(diaminomethynyl)‐1‐ylidene. Four species belonging to the (L→N←L′)⁺ class carrying this unconventional ligand were synthesized. Quantum chemical and X‐ray diffraction analyses showed that the electronic and geometric parameters are consistent with those of already reported divalent N^I compounds. The molecular orbital analysis, geometric parameters, and spectral data clearly support the L→N and N←L′ interactions in these species. The newly identified ligand has the properties of a reactive carbene and high nucleophilicity.