Indyllithium and the Indyl Anion [InL]−: Heavy Analogues of N‐Heterocyclic Carbenes. Issue 20 (14th April 2018)

• Record Type: Journal Article
• Authors: Schwamm, Ryan J.; Anker, Mathew D.; Lein, Matthias; Coles, Martyn P.; Fitchett, Christopher M.
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 20(2018)
• Page Start: 5885
• Page End: 5887
• Publication Date: 2018-04-14
• Subjects: diindanes -- indium -- indyl anions -- main-group chemistry -- N-heterocyclic carbenes; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201802444
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Reduction of the indate complex In(NON Ar )(μ‐Cl)2 Li(OEt2 )2 (NON Ar =[O(SiMe2 NAr)2 ] 2− ; Ar=2, 6‐ i Pr2 C6 H3 ) 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. Abstract : The reduction of indium(III) complexes supported by a chelating bis(amidodimethyl)disiloxane ligand afforded the corresponding In II diindane and the In I indyl anion. The latter was isolated as a non‐contact ion pair with the [K([2.2.2]crypt)] + cation and as the indyllithium complex containing an ionic In−Li bond. These compounds represent the heaviest anionic analogues of N‐heterocyclic carbenes reported to date.