We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
Alkali‐Metal‐Mediated Magnesiations of an N‐Heterocyclic Carbene: Normal, Abnormal, and “Paranormal” Reactivity in a Single Tritopic Molecule.
- Authors
Martínez‐Martínez, Antonio J.; Fuentes, M. Ángeles; Hernán‐Gómez, Alberto; Hevia, Eva; Kennedy, Alan R.; Mulvey, Robert E.; O'Hara, Charles T.
- Abstract
Herein the sodium alkylmagnesium amide [Na4Mg2(TMP)6(nBu)2] (TMP=2,2,6,6‐tetramethylpiperidide), a template base as its deprotonating action is dictated primarily by its 12 atom ring structure, is studied with the common N‐heterocyclic carbene (NHC) IPr [1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene]. Remarkably, magnesiation of IPr occurs at the para‐position of an aryl substituent, sodiation occurs at the abnormal C4 position, and a dative bond occurs between normal C2 and sodium, all within a 20 atom ring structure accommodating two IPr2−. Studies with different K/Mg and Na/Mg bimetallic bases led to two other magnesiated NHC structures containing two or three IPr− monoanions bound to Mg through abnormal C4 sites. Synergistic in that magnesiation can only work through alkali‐metal mediation, these reactions add magnesium to the small cartel of metals capable of directly metalating a NHC.
- Publication
Angewandte Chemie, 2015, Vol 127, Issue 47, p14281
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201507586