Indyllithium and the Indyl Anion [InL] − : Heavy Analogues of N‐Heterocyclic Carbenes

Abstract Reduction of the indate complex In(NON Ar )(μ‐Cl) 2 Li(OEt 2 ) 2 (NON Ar =[O(SiMe 2 NAr) 2 ] 2− ; Ar=2,6‐ i Pr 2 C 6 H 3 ) with sodium generates the In II diindane species [In(NON Ar )] 2 . Further reduction with a mixture of potassium and [2.2.2]crypt affords the In I N‐heterocyclic indyl anion [In(NON Ar )] − , which crystallizes with a non‐contacted [K([2.2.2]crypt)] + cation. The indyl anion can also be isolated as the indyllithium compound In(NON Ar )(Li{THF} 3 ), which contains an In−Li bond. Density functional theory calculations show that the HOMO of the indyl anion is a metal‐centred lone pair, and preliminary reactivity studies confirm its nucleophilic behaviour.