From π-Bonded Gallapnictenes to Nucleophilic, Redox-Active Metal-Coordinated Pnictanides.

A comprehensive reactivity study of gallapnictenes LGaEGa(Cl)L (E=As, Sb; L=HC[C(Me)N(Ar)]2 , Ar=Dip=2,6-i-Pr2 C6 H3 ) proved the nucleophilic character of the pnictogen and the electrophilic nature of the Ga atom. Reactions of LGaEGa(Cl)L with imidazolium chloride [IPrH][Cl] yielded {[LGa(Cl)]2 E- }{IPrH+ } (E=As 1, Sb 2), and those with HCl and MeI gave pnictanes [LGa(Cl)]2 EH (E=As 5, Sb 6) and L(I)GaE(Me)Ga(Cl)L (E=As 7, Sb 8). Pnictanides 1 and 2 also react with [H(OEt2 )2 ][BArF 4 ] (BArF 4 =B(C6 F5 )4 ) to 5 and 6, while reactions with MeI yielded [LGa(Cl)]2 EMe (E=As 9, Sb 10). Single electron oxidation reactions of pnictanides 1 and 2 gave the corresponding radicals [LGa(Cl)]2 E. (E=As, Sb).