Accessing Low‐Valent Inorganic Cations by Using an Extremely Bulky N‐Heterocyclic Carbene

Abstract

Abstract The extremely bulky N‐heterocyclic carbene (NHC), ITr (ITr=[(HCNCPh 3 ) 2 C:]) featuring sterically shielding umbrella‐shaped trityl (CPh 3 ) substituents was prepared. This NHC features the highest percent buried volume (% V bur ) to date, and was used to form a thermally stable quasi one‐coordinate thallium(I) cation [ITr‐Tl] + . This Tl I adduct and the corresponding lithium complex [ITr ⋅ Li(OEt 2 )] + are versatile “all‐in‐one” transmetalation/ligation reagents for preparing low‐coordinate inorganic species inaccessible by pre‐existing routes.