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Indyllithium and the Indyl Anion [InL] − : Heavy Analogues of N‐Heterocyclic Carbenes
Author(s) -
Schwamm Ryan J.,
Anker Mathew D.,
Lein Matthias,
Coles Martyn P.,
Fitchett Christopher M.
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201802444
Subject(s) - chemistry , reactivity (psychology) , lone pair , nucleophile , ion , potassium , density functional theory , medicinal chemistry , stereochemistry , metal , alkali metal , crystallography , computational chemistry , molecule , organic chemistry , catalysis , medicine , alternative medicine , pathology
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.