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

Abstract

A comprehensive reactivity study of gallapnictenes LGaEGa(Cl)L (E=As, Sb; L=HC[C(Me)N(Ar)]2, Ar=Dip=2,6-i-Pr2C6H3) 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)]2E−}{IPrH+} (E=As 1, Sb 2), and those with HCl and MeI gave pnictanes [LGa(Cl)]2EH (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][BArF4] (BArF4=B(C6F5)4) to 5 and 6, while reactions with MeI yielded [LGa(Cl)]2EMe (E=As 9, Sb 10). Single electron oxidation reactions of pnictanides 1 and 2 gave the corresponding radicals [LGa(Cl)]2E. (E=As, Sb).