Trans-Metal-Trapping Meets Frustrated-Lewis-Pair Chemistry: Ga(CH<sub>2</sub>SiMe<sub>3</sub>)<sub>3</sub>‑Induced C–H Functionalizations Marina Uzelac Alan R. Kennedy Eva Hevia 10.1021/acs.inorgchem.7b00549.s001 https://acs.figshare.com/articles/journal_contribution/Trans-Metal-Trapping_Meets_Frustrated-Lewis-Pair_Chemistry_Ga_CH_sub_2_sub_SiMe_sub_3_sub_sub_3_sub_Induced_C_H_Functionalizations/4987214 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 GaR<sub>3</sub> (R = CH<sub>2</sub>SiMe<sub>3</sub>) is paired with the lithium amide LiTMP (TMP = 2,2,6,6-tetramethylpiperidide) or the sterically hindered N-heterocyclic carbene (NHC) 1,3-bis­(<i>tert</i>-butyl)­imidazol-2-ylidene (I<sup><i>t</i></sup>Bu). 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/GaR<sub>3</sub> combination, which on its own fails to form a cocomplex, functions as a highly regioselective base (LiTMP)/trap (GaR<sub>3</sub>) 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 GaR<sub>3</sub> with I<sup><i>t</i></sup>Bu 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. 2017-05-09 17:24:07 compound steric Forum Article group 13 metal activation reagent t Bu Trans-Metal-Trapping Meets Frustrated-Lewis-Pair Chemistry acidic hydrogen atoms TMT metalation lithium amide LiTMP CH 2 SiMe 3 partnership NHC novel monometallic FLP system pairing GaR 3