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.
| Original language | English |
|---|---|
| Pages (from-to) | 14075-14079 |
| Number of pages | 5 |
| Journal | Angewandte Chemie International Edition |
| Volume | 54 |
| Issue number | 47 |
| Early online date | 29 Sep 2015 |
| DOIs | |
| Publication status | Published - 16 Nov 2015 |
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Keywords
- alkali metals
- carbenes
- crown compounds
- magnesium
- metalation
Cite this
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Alkali-metal-mediated magnesiations of an N-heterocyclic carbene : normal, abnormal and "paranormal" reactivity in a single tritopic molecule. / Martínez-Martínez, Antonio J.; Fuentes, M. Ángeles; Hernán-Gõmez, Alberto; Hevia, Eva; Kennedy, Alan R.; Mulvey, Robert E.; O'Hara, Charles T.
In: Angewandte Chemie International Edition, Vol. 54, No. 47, 16.11.2015, p. 14075-14079.Research output: Contribution to journal › Article
TY - JOUR
T1 - Alkali-metal-mediated magnesiations of an N-heterocyclic carbene
T2 - normal, abnormal and "paranormal" reactivity in a single tritopic molecule
AU - Martínez-Martínez, Antonio J.
AU - Fuentes, M. Ángeles
AU - Hernán-Gõmez, Alberto
AU - Hevia, Eva
AU - Kennedy, Alan R.
AU - Mulvey, Robert E.
AU - O'Hara, Charles T.
N1 - This is the peer reviewed version of the following article: Martínez-Martínez, A. J., Fuentes, M. Á., Hernán-Gómez, A., Hevia, E., Kennedy, A. R., Mulvey, R. E. and O'Hara, C. T. (2015), Alkali-Metal-Mediated Magnesiations of an N-Heterocyclic Carbene: Normal, Abnormal, and “Paranormal” Reactivity in a Single Tritopic Molecule. Angew. Chem. Int. Ed., 54: 14075–14079, which has been published in final form at http://dx.doi.org/doi: 10.1002/anie.201507586. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
PY - 2015/11/16
Y1 - 2015/11/16
N2 - 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.
AB - 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.
KW - alkali metals
KW - carbenes
KW - crown compounds
KW - magnesium
KW - metalation
UR - http://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1521-3773
U2 - 10.1002/anie.201507586
DO - 10.1002/anie.201507586
M3 - Article
AN - SCOPUS:84954438503
VL - 54
SP - 14075
EP - 14079
JO - Angewandte Chemie International Edition
JF - Angewandte Chemie International Edition
SN - 1433-7851
IS - 47
ER -