Relative Lability and Chemoselective Transmetallation of NHC in Hybrid Phosphine‐NHC Ligands: Access to Heterometallic Complexes

The relative lability and transmetallation aptitude of trialkylphosphine and NHC donors, integrated in semi-rigid hybrid ligands attached to [Ag4Br4] pseudo-cubanes, lies in favor of the NHC and is used to selectively access unprecedented NHC complexes with heterobimetallic cores, such as Ag-Cu (4(Cy)) and Ag-Ir (5(tBu)). These can be viewed as an arrested state before the full transmetallation of both donors, which gives the homodinuclear Cu (3(Cy)) and Ir (6(Cy)) complexes. The observed NHC transmetallation aptitude and reactivity urges caution in the common notion that views the NHC as a universal spectator.