Multi‐Talented Gallaphosphene for Ga−P−Ga Heteroallyl Cation Generation, CO2 Storage, and C(sp3)−H Bond Activation

Gallaphosphene L(Cl)GaPGaL (2; L=HC[C(Me)N(2,6‐i‐Pr2C6H3)]2), which is synthesized by reaction of LGa(Cl)PCO (1) with LGa, reacts with [Na(OCP)(dioxane)2.5] to LGa(OCP)PGaL (3), whereas chloride ion with LiBArF4 yields [LGaPGaL][BArF4] (4; BArF4=B(C6F5)4). 4 represents a heteronuclear analog of the allyl cation according to quantum chemical calculations. Remarkably, 2 reversibly reacts with CO2 to yield L(Cl)Ga−P[μ‐C(O)O]2GaL (5), while reactions with acetophenone and acetone selectively give compounds 6 and 7 by C(sp3)−H bond activation. Oxidative addition of LGa to a phosphaketene–gallane yields gallaphosphene L(Cl)GaPGaL, from which the heteroallyl cation [LGaPGaL]+ is prepared by a halide ion reaction. Moreover, L(Cl)GaPGaL reversibly reacts with CO2 and selectively activates the C(sp3)−H bond of acetophenone and acetone.