Abstract
| Language | English |
|---|---|
| Number of pages | 12 |
| Journal | Inorganic Chemistry |
| Early online date | 9 May 2017 |
| DOIs | |
| Publication status | E-pub ahead of print - 9 May 2017 |
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Keywords
- gallium
- cooperative chemistry
- trans-metal-trapping
- frustrated lewis pairs
- non-cocomplexing partnerships
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Trans-metal-trapping meets FLP chemistry : Ga(CH2SiMe3)3 induced C-H functionalizations. / Uzelac, Marina; Kennedy, Alan R.; Hevia, Eva.
In: Inorganic Chemistry, 09.05.2017.Research output: Contribution to journal › Article
TY - JOUR
T1 - Trans-metal-trapping meets FLP chemistry
T2 - Inorganic Chemistry
AU - Uzelac, Marina
AU - Kennedy, Alan R.
AU - Hevia, Eva
PY - 2017/5/9
Y1 - 2017/5/9
N2 - Merging two topical themes in Main Group chemistry, namely cooperative bimetallics and FLP activity, this Forum Article focuses on the cooperativity-induced outcomes observed when the tris(alkyl)gallium compound GaR3 (R= CH2SiMe3) is paired with lithium amide LiTMP (TMP=2,2,6,6-tetramethylpiperidide) or the sterically hindered NHC ItBu (ItBu = 1,3-bis(tert-butyl)imidazol-2-ylidene). Drawing together some previously published work with new results, unique tandem reactivities are presented which are driven by the steric mismatch between the individual reagents of these multicomponent reagents. Thus the LiTMP/GaR3 combination, which on its own fails to form a co-complex, functions as a highly regioselective base (LiTMP)-trap (GaR3) partnership for metalation of N-heterocycles such as diazines, 1,3 benzo-azoles and 2-picoline in a trans-metal-trapping (TMT) process that stabilizes the emerging sensitive carbanions. Taking advantage of related steric incompatibility, a novel monometallic FLP system pairing GaR3 with ItBu has been developed for activation of carbonyl compounds (via C=O insertion) and other molecules with acidic hydrogen atoms such as phenol and phenylacetylene. Shedding new light on how these non-cocomplexing partnerships operate and showcasing the potential of Ga reagents to engage in metalation reactions or FLP activations, areas where the use of this Group 13 metal is scant, this Forum Article aims to stimulate more interest and activity towards the advancement of organogallium chemistry.
AB - Merging two topical themes in Main Group chemistry, namely cooperative bimetallics and FLP activity, this Forum Article focuses on the cooperativity-induced outcomes observed when the tris(alkyl)gallium compound GaR3 (R= CH2SiMe3) is paired with lithium amide LiTMP (TMP=2,2,6,6-tetramethylpiperidide) or the sterically hindered NHC ItBu (ItBu = 1,3-bis(tert-butyl)imidazol-2-ylidene). Drawing together some previously published work with new results, unique tandem reactivities are presented which are driven by the steric mismatch between the individual reagents of these multicomponent reagents. Thus the LiTMP/GaR3 combination, which on its own fails to form a co-complex, functions as a highly regioselective base (LiTMP)-trap (GaR3) partnership for metalation of N-heterocycles such as diazines, 1,3 benzo-azoles and 2-picoline in a trans-metal-trapping (TMT) process that stabilizes the emerging sensitive carbanions. Taking advantage of related steric incompatibility, a novel monometallic FLP system pairing GaR3 with ItBu has been developed for activation of carbonyl compounds (via C=O insertion) and other molecules with acidic hydrogen atoms such as phenol and phenylacetylene. Shedding new light on how these non-cocomplexing partnerships operate and showcasing the potential of Ga reagents to engage in metalation reactions or FLP activations, areas where the use of this Group 13 metal is scant, this Forum Article aims to stimulate more interest and activity towards the advancement of organogallium chemistry.
KW - gallium
KW - cooperative chemistry
KW - trans-metal-trapping
KW - frustrated lewis pairs
KW - non-cocomplexing partnerships
UR - http://pubs.acs.org/loi/inocaj
U2 - 10.1021/acs.inorgchem.7b00549
DO - 10.1021/acs.inorgchem.7b00549
M3 - Article
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
ER -