Synthesis of N‐Heterocyclic Carbenes and Their Complexes by Chloronium Ion Abstraction from 2‐Chloroazolium Salts Using Electron‐Rich Phosphines

N‐Heterocyclic carbenes (NHCs) are commonly prepared by deprotonation of azolium salts using strong anionic bases. This reaction is often unselective, yielding alkali metal NHC complexes or dimerized NHCs. Alternatively, free NHCs are obtained by the dechlorination of 2‐chloroazolium salts using electron‐rich phosphines. PPh(3), PCy(3), and PtBu(3) are unsuitable for Cl(+) abstraction, while the sterically encumbered tris(1,3‐tert‐butylimidazolidin‐2‐ylidenamino)phosphine 1 selectively removes Cl(+) from 2‐chloroazolium salts. Since bulky 1 does not bind to metal complexes, it was used for the preparation of NHC complexes via in situ Cl(+) abstraction from 2‐chloroazolium salts. The dechlorination was employed for the site‐selective monometallation with Ir(I), Ir(III), Rh(I), Rh(III), and Ru(II) of a bis‐NHC precursor composed of a 2‐chlorobenzimidazolium and a 2‐chlorobenzimidazole group, followed by the preparation of the heterobimetallic Ir(III)/Pd(II) complex [18](BF(4))(2) by a dechlorination/oxidative addition reaction sequence.