Reactions of Gallaphosphaketenes with Silylenes: Formation of Gallaphosphenes versus Silaphosphenes

Heavy main group element compounds with heteronuclear double bonds are of interest due to their fascinating reactivity. Herein, the synthesis of silaphosphenes L 1 Ga(X)PSiL 2 (X = Cl 2a , Me 2b , L 1 = [N(Dipp)C(Me)] 2 CH, Dipp = 2,6‐ i Pr 2 C 6 H 3 ; L 2 = PhC(N t Bu) 2 ) and L 1 Ga(Cl)PSiL 4 4 (L 4 = [N(Dipp)C(Me)] 2 ) is reported, which are obtained from reactions of gallaphosphaketenes L 1 Ga(X)PCO (X = Cl 1a , Me 1b ) with silylenes L 2 SiCl and the N‐heterocyclic silylene L 4 Si, respectively. In contrast, gallaphosphene L 1 GaPSi(Cl)L 3 3 (L 3 = DippNC(CH 3 )CHC(CH 2 )NDipp) formed in the reaction of 1a with the β‐diketiminate‐substituted silylene L 3 Si. Silaphosphenes 2a and 4 and gallaphosphene 3 are promising reagents for reactions with nucleophiles and electrophiles as is exemplarily demonstrated with HCl, MeI, MeOTf, MeLi, BnOH, BnNC, and CO 2 , respectively.