Electronic Properties of N‑Heterocyclic Carbenes and Their Experimental Determination

N-Heterocyclic carbenes (NHCs) have become without doubt one of the most exciting and popular species in chemical science due to the ease of their preparation and modularity in stereoelectronic properties. Numerous types of NHCs have been prepared, and various experimental methodologies have been proposed for the study of their electronic properties in order to rationalize reactivities observed. The objective of this article is to provide a comprehensive overview of the most common and popular ones among them. In particular, these include the nickel­(0)-based TEP, its rhodium­(I) and iridium­(I) variants, LEP and related electrochemical methods, the palladium­(II)-based HEP, phosphinidene- and selenourea-based methods, as well as the use of direct 1 J(C–H) coupling constants of the precarbene carbon in azolium salts. Each individual method and the underlying principle of detection it utilizes will be critically discussed in terms of strength and weakness. In addition, comprehensive amounts of data from various NHCs are compiled for the purpose of comparison. These are also meant to help the scientist in better understanding their own research data and possibly providing directions for their future research, which rely on the unique electronic properties of NHCs.