Abstract
Merging two topical themes in main-group chemistry, namely, cooperative bimetallics and frustrated-Lewis-pair (FLP) activity, this Forum Article focuses on the cooperativity-induced outcomes observed when the tris(alkyl)gallium compound GaR3 (R = CH2SiMe3) is paired with the lithium amide LiTMP (TMP = 2,2,6,6-tetramethylpiperidide) or the sterically hindered N-heterocyclic carbene (NHC) 1,3-bis(tert-butyl)imidazol-2-ylidene (ItBu). When some previously published work are drawn together with new results, unique tandem reactivities are presented that 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 cocomplex, functions as a highly regioselective base (LiTMP)/trap (GaR3) partnership for the metalation of N-heterocycles such as diazines, 1,3-benzoazoles, and 2-picolines 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 the 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 gallium 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 toward the advancement of organogallium chemistry.
Original language | English |
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Pages (from-to) | 8615-8626 |
Number of pages | 12 |
Journal | Inorganic Chemistry |
Volume | 56 |
Issue number | 15 |
DOIs | |
Publication status | Published - 7 Aug 2017 |
Bibliographical note
Funding Information:The European Research Council (ERC) MIXMETAPPS- 279590 FP7 project and the EPSRC project "Towards a Paradigm Shift in the Principles and Practice of Polar Organometallic Chemistry", grant number EP/N011384/1.
Funding
The European Research Council (ERC) MIXMETAPPS- 279590 FP7 project and the EPSRC project "Towards a Paradigm Shift in the Principles and Practice of Polar Organometallic Chemistry", grant number EP/N011384/1.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry