Can Remote N‐Heterocyclic Carbenes Coordinate with Main Group Elements? Synthesis, Structure, and Quantum Chemical Analysis of N⁺‐Centered Complexes

Abstract

Remote N-heterocyclic carbenes (rNHCs), such as N-methyl-4-pyridylidene, are known to form coordination complexes with TMs. Herein, it is established that rNHCs can also coordinate to the N⁺ centre. Synthesis of some novel divalent N^I complexes with the general formula (rNHC)→N⁺ ←(NHC) and (rNHC)→N⁺ ←(rNHC) was achieved, and X-ray diffraction studies supported the coordination bond character between the rNHCs and the N⁺ centre. Quantum chemical analysis established the presence of divalent N^I character at the central nitrogen in these systems.