Synthesis and Reactivity of Heteroleptic Ga‐P‐C Allyl Cation Analogues

Oxidative addition of cyclic alkyl(amino)carbene‐coordinated phosphinidenes ( Me cAAC)PX to LGa affords gallium‐coordinated phosphinidenes LGa(X)‐P( Me cAAC) (L=HC[C(Me)N(2,6‐ i ‐Pr 2 C 6 H 3 )] 2 ; X=Cl 1 , Br 2 ), which react with NaBAr F 4 and LiAl(OR F ) 4 to [LGaP( Me cAAC)][An] (An=B(C 6 H 3 (CF 3 ) 2 ) 4 3 , B(C 6 F 5 ) 4 4 , Al(OC(CF 3 ) 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 .