Anionic N‐heterocyclic carbenes that bear a weakly coordinating fluoroborate moiety have been used to prepare a new class of anionic imidazolin‐2‐thione and ‐selone ligands; their coordination chemistry towards rhodium and iridium was explored to reveal their ability to develop secondary arene–metal interactions with the “wings” of the carbene ligands. More information about these new additions to the family of chalcogenolate ligands and their potential future application in coordination chemistry, bioinorganic chemistry and homogeneous catalysis can be found in the Research Article by M. Tamm et al. (DOI: 10.1002/chem.202104139).

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 metalchalcogen π-interaction.