Rhodium and Iridium Complexes of Anionic Thione and Selone Ligands Derived from Anionic N‐Heterocyclic Carbenes

The lithium salts of anionic N‐heterocyclic thiones and selones [{(WCA‐IDipp)E}Li(toluene)] (1: E=S; 2: E=Se; WCA=B(C(6)F(5))(3), IDipp=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene), which contain a weakly coordinating anionic (WCA) borate moiety in the imidazole backbone were reacted with Me(3)SiCl, to furnish the silylated adducts (WCA‐IDipp)ESiMe(3) (3: E=S; 4: E=Se). The reaction of the latter with [(η (5)‐C(5)Me(5))MCl(2)](2) (M=Rh, Ir) afforded the rhodium(III) and iridium(III) half‐sandwich complexes [{(WCA‐IDipp)E}MCl(η (5)‐C(5)Me(5))] (5–8). The direct reaction of the lithium salts 1 and 2 with a half or a full equivalent of [M(COD)Cl](2) (M=Rh, Ir) afforded the monometallic complexes [{(WCA‐IDipp)E}M(COD)] (9–12) or the bimetallic complexes [μ (2)‐{(WCA‐IDipp)E}M(2)(COD)(2)(μ (2)‐Cl)] (13–16), respectively. The bonding situation in these complexes has been investigated by means of density functional theory (DFT) calculations, revealing thiolate or selenolate ligand character with negligible metal‐chalcogen π‐interaction.