Trans-Metal-Trapping Meets Frustrated-Lewis-Pair Chemistry: Ga(CH₂SiMe₃)₃‑Induced C–H Functionalizations

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 (I^tBu). 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 I^tBu 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.