Abstract
Oxidative addition of cyclic alkyl(amino)carbene‐coordinated phosphinidenes (MecAAC)PX to LGa affords gallium‐coordinated phosphinidenes LGa(X)‐P(MecAAC) (L=HC[C(Me)N(2,6‐i‐Pr2C6H3)]2; X=Cl 1, Br 2), which react with NaBArF 4 and LiAl(ORF)4 to [LGaP(MecAAC)][An] (An=B(C6H3(CF3)2)4 3, B(C6F5)4 4, Al(OC(CF3)3)4 5). The cations in 3–5 show substantial Ga−P double bond character and represent heteronuclear analogues of allyl cations according to quantum chemical calculations. The reaction of 4 with 4‐dimethylaminopyridine (dmap) to adduct 6 confirms the strong electrophilic nature of the gallium center, whereas 5 reacts with ethyl isocyanate with C−C bond formation to the γ‐C atom of the β‐diketiminate ligand and formation of compound 7.
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