Chalcogen‐Pnictogen Complexes of Anionic N‐Heterocyclic Carbenes with a Weakly Coordinating Borate Moiety

Chalcogen‐pnictogen dihalide complexes which bear an anionic N‐heterocyclic carbene ligand with a tethered weakly coordinating borate moiety (WCA‐IDipp, WCA=B(C 6 F 5 ) 3 , IDipp=1,3‐bis(2,6‐diisopropyphenyl)imidazolin‐2‐ylidene) were isolated and fully characterized. The metathesis reaction between the lithium salts [{(WCA‐IDipp)E}Li(toluene)] (E=S, Se) and pnictogen trihalides E′X 3 (E=P, As, Sb; X=Cl, Br) afforded the complexes of the general type (WCA‐IDipp)E−E′X 2 (E=S, Se; E=P, As, Sb; X=Cl, Br). In contrast, lithium chloride elimination was not observed with BiCl 3 under the same reaction conditions and instead, the lithium complexes [{(WCA‐IDipp)E−BiCl 3 }Li(thf) 4 ] (E=S, Se) were obtained. However, the corresponding bismuth dichloride derivatives (WCA‐IDipp)E−BiCl 2 were accessible from the reaction of (WCA‐IDipp)ESiMe 3 with BiCl 3 upon Me 3 SiCl elimination.